Organic electrolumescence device

ABSTRACT

Materials for organic electroluminescence devices are represented by following general formula [1]:  
                 
         wherein A represents a chrysene group, X 1  to X 4  each independently represent a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, X 1  and X 2  may be bonded to each other, X 3  and X 4  may be bonded to each other, Y 1  to Y 4  each independently represent an organic group represented by general formula [2], a to d each represent an integer of 0 to 2 and, a+b+c+d≧0; 
 
general formula [2] being:  
                 
   wherein R 1  to R 4  each independently represent hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, cyano group or form a triple bond by a linkage of R 1  and R 2  or R 3  and R 4 , Z represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and n represents 0 or 1.

REFERENCE TO PRIOR APPLICATIONS

This application is a Continuation of U.S. application Ser. No.11/344,604, filed Feb. 1, 2006; which is a Continuation of U.S.application Ser. No. 10/814,121, filed Apr. 1, 2004, now abandoned;which is a Division of U.S. application Ser. No. 09/623,057, nowpatented; which is a 371 of PCT/JP99/07390, filed Dec. 28, 1999.

TECHNICAL FIELD

The present invention relates to materials for organicelectroluminescence devices which are used as a light source such as aplanar light emitting member of televisions and a back light ofdisplays, exhibit high efficiency of light emission and have excellentheat resistance and a long life, organic electroluminescence devicesusing the materials, novel compounds and processes for producingmaterials for electroluminescence devices.

BACKGROUND ART

Electroluminescence (EL) devices using organic compounds are expected tobe used for inexpensive full color display devices of the solid lightemission type which can display a large area and development thereof hasbeen actively conducted. In general, an EL device is constituted with alight emitting layer and a pair of electrodes faced to each other atboth sides of the light emitting layer. When a voltage is appliedbetween the electrodes, electrons are injected at the side of thecathode and holes are injected at the side of the anode. The electronsare combined with the holes in the light emitting layer and an excitedstate is formed. When the excited state returns to the normal state, theenergy is emitted as light.

Heretofore, organic EL devices require higher driving voltages and showinferior luminance of emitted light and inferior efficiencies of lightemission in comparison with inorganic devices. Moreover, properties oforganic EL devices deteriorate very rapidly. Therefore, heretofore,organic EL devices have not been used practically. Although theproperties of organic EL devices have been improved, organic EL devicesexhibiting a sufficient efficiency of light emission and havingsufficient heat resistance and life have not been obtained. For example,a phenylanthracene derivative which can be used for EL devices isdisclosed in Japanese Patent Application Laid-Open No. Heisei8(1996)-12600. However, an organic EL device using this compoundexhibited an efficiency of light emission as low as about 2 to 4 cd/Aand improvement in the efficiency is desired. In Japanese PatentApplication Laid-Open No. Heisei 8(1996)-199162, an EL device having alight emitting layer containing a fluorescent dopant of a derivative ofan amine or a diamine is disclosed. However, this EL device has a lifeas short as 700 hours at an initial luminance of emitted light of 300cd/m² although the efficiency of light emission is 4 to 6 dc/A andimprovement in the life is desired. In Japanese Patent ApplicationLaid-Open No. Heisei 9(1997)-268284, a material for EL devices havingphenylanthracene group is disclosed. This material exhibits a markeddecrease in the luminance of emitted light when the material is used ata high temperature for a long time and heat resistance is insufficient.Moreover, these devices do not emit light in the region of orange to redcolor. Since emission of red color is indispensable for the full colordisplay by an EL device, a device emitting light in the region of orangeto red color is desired. When these materials are used as the hostmaterial and other compounds are used as the doping material, a longlife cannot be obtained. It is necessary for practical use that aninitial luminance of emitted light of 10,000 d/m² or greater beexhibited. However, this value has not been achieved. In Japanese PatentApplication Laid-Open No. Heisei 11(1999)-152253, an example isdisclosed in which a material for organic EL devices having abinaphthalene structure is added to a light emitting layer having theproperty to transfer electrons such as a layer of an aluminum complex orthe like. However, in this example, the aluminum complex or the likeemits light and the material for organic EL devices does not function asthe light emitting center since the energy gap of the light emittinglayer of the aluminum complex or the like is smaller than the energy gapof the material for organic EL devices.

Synthesis of arylamines used as a material for organic EL devices hasbeen conducted by the Ullmann reaction using an amine and aniodobenzene. It is described, for example, in Chem. Lett., pp. 1145 to1148, 1989; the specification of U.S. Pat. No. 4,764,625; and JapanesePatent Application Laid-Open No. Heisei 8(1996)-48974 that atriarylamine is produced by the reaction of a corresponding iodobenzeneand a diarylamine in an inert hydrocarbon solvent such as decaline at150° C. or higher in the presence of one equivalent or more of copperpowder and a base such as potassium hydroxide as the typical example.

However, the process using the Ullmann reaction has drawbacks in that anexpensive iodide must be used as the reacting agent, that the reactioncannot be applied to many types of compounds, that the yield of thereaction is not sufficient, that the reaction requires a temperature ashigh as 150° C. and a long time and that waste liquid containing a greatamount of copper is formed since copper powder is used in a great amountand environmental problems arise.

DISCLOSURE OF THE INVENTION

The present invention has been made to overcome the above problems andhas an object to provide a material for organic electroluminescencedevices, an organic electroluminescence device and a novel compoundwhich exhibit high efficiency of light emission and have a long life andexcellent heat resistance and a process for producing the material fororganic electroluminescence devices.

As the result of extensive studies by the present inventors to developthe material for organic EL devices having the advantageous propertiesdescribed above and an organic EL device using the material, it wasfound that the object can be achieved by using the compounds representedby general formulae [1] and [3] to [10] which are shown below. Thepresent invention has been completed based on this knowledge.

It was also found by the present inventors that the above object can beachieved by using the compounds represented by general formulae [11] and[11′] as the doping material or the light emitting center.

It was further found by the present inventors that a tertiary arylaminewhich is a material for organic EL devices can be synthesized with ahigh activity by the reaction of an amine and an aryl halide in thepresence of a catalyst comprising a phosphine compound and a palladiumcompound and a base. The present invention has been completed based onthe above knowledge.

The material for organic electroluminescence devices (referred to as thematerial for organic EL devices) of the present invention is a compoundrepresented by following general formula [1]:

wherein A represents a substituted or unsubstituted arylene group having22 to 60 carbon atoms, X¹ to X⁴ each independently represent asubstituted or unsubstituted arylene group having 6 to 30 carbon atoms,X¹ and X² may be bonded to each other, X³ and X⁴ may be bonded to eachother, Y¹ to Y⁴ each independently represent an organic grouprepresented by general formula [2], a to d each represent an integer of0 to 2 and, when the arylene group represented by A has 26 or lesscarbon atoms, a+b+c+d>0 and the arylene group does not contain two ormore anthracene nuclei; general formula [2] being:

wherein R¹ to R⁴ each independently represent hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group or form a triple bond by a linkage of R¹ and R² or R³ andR⁴, Z represents a substituted or unsubstituted aryl group having 6 to20 carbon atoms and n represents 0 or 1.

The material for organic electroluminescence devices of the presentinvention may also be a compound represented by following generalformula [3]:

wherein B represents a substituted or unsubstituted arylene group having6 to 60 carbon atoms, X¹ to X⁴ each independently represent asubstituted or unsubstituted arylene group having 6 to 30 carbon atoms,X¹ and X² may be bonded to each other, X³ and X⁴ may be bonded to eachother, Y¹ to Y⁴ each independently represent an organic grouprepresented by general formula [2] described above, a to d eachrepresent an integer of 0 to 2 and at least one of groups represented byB, X¹, X², X³ and X⁴ has a chrysene nucleus.

It is preferable that general formula [3] means following generalformula [4], general formula [5] or general formula [6].

wherein X¹ to X⁴, Y¹ to Y⁴ and a to d are each independently the same asthose in general formula [3].

wherein B, X¹, X², Y¹, Y², a and b are each independently the same asthose in general formula [3].

wherein B, X¹, X², Y¹, Y², a and b are each independently the same asthose in general formula [3].

The material for organic electroluminescence devices of the presentinvention may also be a compound represented by following generalformula [7]:

wherein D represents a divalent group having a tetracene nucleus or apentacene nucleus, X¹ to X⁴ each independently represent a substitutedor unsubstituted arylene group containing 6 to 30 carbon atoms, X¹ andX² may be bonded to each other, X³ and X⁴ may be bonded to each other,Y¹ to Y⁴ each independently represent an organic group represented bygeneral formula [2] described above and a to d each represent an integerof 0 to 2.

It is preferable that general formula [7] means following generalformula [8]:

wherein X¹ to X⁴, Y¹ to Y⁴ and a to d are each independently the same asthose in general formula [7], R⁵¹ to R⁶⁰ each independently representhydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20carbon atoms, a substituted or unsubstituted aryl group having 6 to 20carbon atoms or cyano group and adjacent groups among the groupsrepresented by R⁵¹ to R⁶⁰ may be bonded to each other to form asaturated or unsaturated and substituted or unsubstituted carbon ring.

The material for organic electroluminescence devices of the presentinvention may also be a compound represented by following generalformula [9]:

wherein E represents a divalent group comprising an anthracene nucleuswhich is substituted with aryl groups or unsubstituted, X⁵ to X⁸ eachindependently represent a substituted or unsubstituted arylene grouphaving 6 to 20 carbon atoms, X⁵ and X⁶ may be bonded to each other, X⁷and X⁸ may be bonded to each other, Y¹ to Y⁴ each independentlyrepresent an organic group represented by general formula [2], a to deach represent an integer of 0 to 2, and when the group represented by Eis an unsubstituted group:

at least two of X⁵ to X⁸ contains a substituted or unsubstituted group:

The material for organic electroluminescence devices of the presentinvention may also be a compound represented by following generalformula [10]:

wherein Ar¹ and Ar³ each independently represents a divalent groupselected from a group consisting of substituted and unsubstitutedphenylene groups, substituted and unsubstituted 1,3-naphthalene groups,substituted and unsubstituted 1,8-naphthalene groups, substituted andunsubstituted fluorene groups and substituted and unsubstituted biphenylgroups, Ar² represents a divalent group selected from a group consistingof substituted and unsubstituted anthracene nuclei, substituted andunsubstituted pyrene nuclei, substituted and unsubstituted phenanthrenenuclei, substituted and unsubstituted chrysene nuclei, substituted andunsubstituted pentacene nuclei, substituted and unsubstitutednaphthacene nuclei and substituted and unsubstituted fluorene nuclei, X⁵to X⁸ each independently represent a substituted or unsubstitutedarylene group having 6 to 20 carbon atoms, X⁵ and X⁶ may be bonded toeach other, X⁷ and X⁸ may be bonded to each other, Y¹ to Y⁴ eachindependently represent an organic group represented by general formula[2] described above, a to d each represent an integer of 0 to 2,a+b+c+d≦2, e represents 0 or 1, f represents 1 or 2 and, when Ar²represents an anthracene nucleus, a case in which a=b=c=d and Ar¹ andAr³ both represent p-phenylene group is excluded.

The material for organic electroluminescence devices of the presentinvention may also be a compound represented by following generalformula [11]:

wherein F represents a substituted or unsubstituted arylene group having6 to 21 carbon atoms, X¹ to X⁴ each independently represent asubstituted or unsubstituted arylene group having 6 to 30 carbon atoms,X¹ and X² may be bonded to each other, X³ and X⁴ may be bonded to eachother, Y¹ to Y⁴ each independently represent an organic grouprepresented by general formula [2] described above, a to d eachrepresent an integer of 0 to 2, and a+b+c+d>0.

It is preferable that the group represented by F in general formula [11]is a group represented by following general formula [12], generalformula [13] or general formula [14]:

wherein R^(5′) to R^(24′) each independently represent hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group and adjacent groups among the groups represented by R^(5′)to R^(24′) my be bonded to each other to form a saturated or unsaturatedcarbon ring;

wherein R^(25′) to R^(34′) each independently represent hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group and adjacent groups among the groups represented by R^(5′)to R^(24′) my be bonded to each other to form a saturated or unsaturatedcarbon ring.

The material for organic EL devices of the present invention which isrepresented by any of general formulae [1], [3] to [11] and [11′] can beused also as the light emitting material for organic electroluminescencedevices.

The organic electroluminescence (EL) device of the present inventioncomprises a light emitting layer or a plurality of thin films of organiccompounds comprising a light emitting layer disposed between a pair ofelectrodes, wherein at least one of the thin films of organic compoundsis a layer comprising a materials for organic EL devices represented byany of general formulae [1], [3] to [11] and [11′].

It is preferable that, in the above organic EL device, a layercomprising the material for organic EL devices represented by any ofgeneral formulae [1], [3] to [11] and [11′] as at least one materialselected from a group consisting of a hole injecting material, a holetransporting material and a doping material is disposed between the pairof electrodes It is preferable that, in the above organic EL device, thelight emitting layer comprises 0.1 to 20% by weight of a material fororganic EL devices represented by any of general formulae [1], [3] to[11] and [11′].

It is preferable that, in the above organic electroluminescence device,one or more materials selected from a group consisting of a holeinjecting material, a hole transporting material and a doping materialeach independently comprise 0.1 to 20% by weight of the material fororganic EL devices represented by any of general formulae [1], [3] to[11] and [11′].

It is preferable that, in the above organic EL device, the lightemitting layer is a layer comprising a stilbene derivative and amaterial for organic EL devices represented by any of general formulae[1], [3] to [11] and [11′].

In the above organic EL device, a layer comprising an aromatic tertiaryamine derivative and/or a phthalocyanine derivative is disposed betweena light emitting layer and an anode.

It is preferable that, in the above organic EL device, the energy gap ofthe material for organic electroluminescence devices represented bygeneral formula [11] is smaller than the energy gap of a host materialby 0.07 eV or greater.

The novel compound of the present invention is represented by followinggeneral formula [11′]:

wherein F represents a group represented by general formula [14], X¹ toX⁴ each independently represent a substituted or unsubstituted arylenegroup having 6 to 30 carbon atoms, X¹ and X² may be bonded to eachother, X³ and X⁴ may be bonded to each other, Y¹ to Y⁴ eachindependently represent an organic group represented by general formula[2] described above, a to d represent each an integer of 0 to 2, anda+b+c+d>0; general formula [14] being:

wherein R^(25′) to R^(34′) each independently represent hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group and adjacent groups among the groups represented by R^(5′)to R^(24′) my be bonded to each other to form a saturated or unsaturatedcarbon ring.

The process for producing a material for organic EL devices of thepresent invention comprises reacting, in a presence of a catalystcomprising a phosphine compound and a palladium compound and a base, aprimary amine or a secondary amine represented by following generalformula [15]:R(NR′H)_(k)  [15]wherein k represents an integer of 1 to 3; when k represents 1, R and R′represent hydrogen atom, an alkyl group or a substituted orunsubstituted aryl group; and when k represents 2 or 3, R represents analkylene group or substituted or unsubstituted arylene group and R′represents hydrogen atom, an alkyl group or a substituted orunsubstituted aryl group, with an aryl halide represented by followinggeneral formula [16]:Ar(X)_(m)  [16]wherein Ar represents a substituted or unsubstituted aryl group, Xrepresents F, Cl, Br or I and m represents an integer of 1 to 3, andproducing a material for organic electroluminescence devices comprisingan arylamine compound.

It is preferable that the arylamine described above is a compoundrepresented by following general formula [17]:

wherein F represents a substituted or unsubstituted arylene group having6 to 60 carbon atoms, X¹ to X⁴ each independently represent asubstituted or unsubstituted arylene group having 6 to 30 carbon atoms,X¹ and X² may be bonded to each other, X³ and X⁴ may be bonded to eachother, Y¹ to Y⁴ each independently represent an organic grouprepresented by general formula [2] described above, a to d eachrepresent an integer of 0 to 2, and a+b+c+d>0.

It is preferable that the phosphine compound is a trialkylphosphinecompound, a triarylphosphine compound or a diphosphine compound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a ¹H_(NMR) chart of compound a synthesized in accordancewith the process of the present invention.

FIG. 2 shows a ¹H_(NMR) chart of compound b synthesized in accordancewith the process of the present invention.

FIG. 3 shows a ¹H_(NMR) chart of compound e synthesized in accordancewith the process of the present invention.

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

In general formula [1] in the present invention, A represents asubstituted or unsubstituted arylene group having 22 to 60 carbon atoms.Examples of the arylene group include divalent groups formed frombiphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene,fluorene, thiophene, coronene and fluoranthene and divalent groupsformed by bonding a plurality of these groups to each other. X¹ to X⁴ ingeneral formula [1] each independently represent a substituted orunsubstituted arylene group having 6 to 30 carbon atoms. Examples of thegroup represented by X¹ to X⁴ include monovalent or divalent groupscontaining skeleton structures of phenyl, biphenyl, terphenyl,naphthalene, anthrathene, phenanthrene, pyrene, fluorene, thiophene,coronene and chrysene. X¹ and X² may be connected to each other and X³and X⁴ may be connected to each other.

The groups used as the substituents to the groups represented by X¹ toX⁴ are each independently an alkyl group having 1 to 20 carbon atoms, analkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20carbon atoms. Aryloxy groups, arylthio groups, arylalkyl groups and arylketone groups are excluded from the above substituent because compoundshaving the groups excluded above tend to decompose under heating invapor deposition and the life of the obtained device is short.

In general formula [1], a to d each represent an integer of 0 to 2.However, when the group represented by A has 26 or less carbon atoms,a+b+c+d>0 and the group represented by A does not contain 2 or moreanthracene nuclei.

In general formula [2] in the present invention, R¹ to R⁴ eachindependently represent hydrogen atom, a substituted or unsubstitutedalkyl group having 1 to 20 carbon atoms, a substituted or unsubstitutedaryl group having 6 to 20 carbon atoms or cyano group. Examples of thegroup represented by R¹ to R⁴ include substituted and unsubstitutedalkyl groups such as methyl group, ethyl group, propyl group, butylgroup, sec-butyl group, tert-butyl group, pentyl group, hexyl group,heptyl group, octyl group, stearyl group, 2-phenylisopropyl group,trichloromethyl group, trifluoromethyl group, benzyl group,α-phenoxybenzyl group, α,α-dimethylbenzyl group, α,α-methylphenylbenzylgroup, α,α-ditrifluoromethylbenzyl group, triphenylmethyl group andα-benzyloxybenzyl group; and substituted and unsubstituted aryl groupssuch as phenyl group, 2-methylphenyl group, 3-methylphenyl group,4-methylphenyl group, 4-ethylphenyl group, biphenyl group,4-methylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexylbiphenylgroup, terphenyl group, 3,5-dichlorophenyl group, naphthyl group,5-methylnaphthyl group, anthryl group and pyrenyl group.

In general formula [2] in the present invention, Z represents asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms.Examples of the group represented by Z include aryl groups such asphenyl group, biphenyl group, terphenyl group, naphthyl group, anthrylgroup, phenanthryl group, fluorenyl group, pyrenyl group and thiophenegroup. The above aryl groups may have substituents. Examples of thesubstituent include alkyl groups and aryl groups described above as theexamples of the group represented by R¹ to R⁴, alkoxy groups, aminogroup, cyano group, hydroxyl group, carboxylic acid group, ether groupand ester groups. In general formula [2], n represents 0 or 1.

As described above, since the compound represented by general formula[1] in the present invention has a diamine structure at the centralportion and a styrylamine structure at end portions, the ionizationenergy is 5.6 eV or smaller and holes can be easily injected. Themobility of holes is 10⁻⁴ m²/V·s or greater. Therefore, the compound hasthe excellent properties as the hole injecting material and the holetransporting material. Due to the polyphenyl structure at the center,the electron affinity is 2.5 eV or greater and electrons can be easilyinjected.

Moreover, since the structure represented by A has 22 or more carbonatoms, an amorphous thin film can be easily formed. The glass transitiontemperature is raised to 100° C. or higher and heat resistance can beimproved. When two or more anthracene groups are contained in thestructure represented by A, there is the possibility that the compoundrepresented by general formula [1] decomposes under heating.

Compounds having a structure in which X¹ and X² or X³ and X⁴ are bondedto each other through a single bond or a carbon ring bond has elevatedglass transition temperatures and show improved heat resistance.

In the compounds represented by general formulae [3] to [6] of thepresent invention, B represents a substituted or unsubstituted arylenegroup having 6 to 60 carbon atoms. Examples of the group represented byB include divalent groups formed from biphenyl, terphenyl, naphthalene,anthracene, phenanthrene, pyrene, fluorene, thiophene, coronene andfluoranthene and divalent groups formed by bonding a plurality of thesegroups to each other. X¹ to X⁴, Y¹ to Y⁴ and a to d are the same asthose in general formula [1], wherein at least one of the groupsrepresented by B, X¹, X², X³ and X⁴ has a chrysene nucleus.

As described above, since the compounds represented by general formulae[3] to [6] in the present invention have a diamine structure at thecentral portion and a styrylamine structure at end portions, theionization energy is 5.6 eV or smaller and holes can be easily injected.The mobility of holes is 10⁻⁴ m²/V·s or greater. Therefore, the compoundhas the excellent properties as the hole injecting material and the holetransporting material. Due to the chrysene nucleus contained in at leastone of the groups represented by B, X¹, X², X³ and X⁴, durability andheat resistance are improved. Therefore, driving for a long time isenabled and an organic EL device which can be stored or driven at hightemperatures can be obtained.

Moreover, the life of the organic EL device can be extended when thecompounds represented by general formulae [3] to [6] are used as thedoping material and the efficiency of light emission can be improvedwhen the compounds are used as the material of the light emitting layer.

In the compound represented by general formula [7] of the presentinvention, D represents a divalent group containing a substituted orunsubstituted tetracene nucleus or pentacene nucleus. Examples of thegroup represented by D include divalent groups formed by connecting aplurality of at least one group selected from the group consisting ofbiphenyl, naphthalene, anthracene, phenanthrene, fluorene and thiopheneand the tetracene nucleus or the pentacene nucleus. X¹ to X⁴, Y¹ to Y⁴and a to d are the same as those in general formula [1], wherein X¹ andX² may be bonded to each other and X³ and X⁴ may be bonded to eachother.

In the compound represented by general formula [8] of the presentinvention, X¹ to X⁴, Y¹ to Y⁴ and a to d each independently representthe same atom and groups as those described above in general formula[1]. R⁵¹ to R⁶⁰ each independently represent hydrogen atom, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, asubstituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group and adjacent groups among the groups represented by R⁵¹ toR⁶⁰ may be bonded to each other to form a saturated or unsaturated andsubstituted or unsubstituted carbon ring.

The groups used as the substituent in general formulae [7] and [8] areeach independently an alkyl group having 1 to 20 carbon atoms, an alkoxygroup having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbonatoms. Aryloxy groups, arylthio groups, arylalkyl groups and aryl ketonegroups are excluded from the above substituent because compounds havingthe groups excluded above tend to decompose under heating in vapordeposition and the life of the obtained device is short.

As described above, the compound represented by general formula [7] inthe present invention exhibits strong fluorescence in the region oforange to red color due to the tetracene or pentacene structure. Holesare easily injected due to the diamine structure. When this compound iscontained in the light emitting layer, holes are easily trapped andrecombination of electrons and holes is promoted. Therefore, a lightemitting device emitting yellow color, orange color and red color in ahigh efficiency can be obtained.

In particular, when the compound represented by general formula [7] isused as the doping material, the obtained light emitting device has along life and exhibits more excellent stability than that exhibited byany conventional devices.

In the compound represented by general formula [9] in the presentinvention, E represents a divalent group comprising an anthracenenucleus which is substituted with aryl groups or unsubstituted. X⁵ to X⁸each independently represent a substituted or unsubstituted arylenegroup having 6 to 20 carbon atoms. Examples of the group represented byX⁵ to X⁸ include monovalent and divalent groups containing the skeletonstructure of phenylene, biphenyl, terphenyl, naphthalene, anthracene,phenanthrene, fluorene and thiophene. X⁵ and X⁶ may be bonded to eachother and X⁷ and X⁸ may be bonded to each other. Y¹ to Y⁴ and a to d arethe same as those in general formula [1].

However, when E represents an unsubstituted group:

at least two of X⁵ to X⁸ contain a substituted or unsubstituted group:

As described above, since the compound represented by general formula[9] in the present invention has a diamine structure, the ionizationenergy is 5.6 eV or smaller and holes can be easily injected. Themobility of holes is 10⁻⁴ m²/V·s or greater. Therefore, the compound hasthe excellent properties as the hole injecting material and the holetransporting material. Due to the substituted or unsubstitutedanthracene nucleus at the center, electrons are easily injected.

When the anthracene nucleus represented by E is unsubstituted, the glasstransition temperature is as low as 100° C. or lower. The glasstransition temperature can be elevated by bonding at least twosubstituents and preferably 2 to 4 substituents to the nucleus asdescribed above. The specific biphenyl structure described aboveenhances solubility of the compound represented by general formula [9]and purification can be facilitated. When phenyl group is bonded at aposition other than the above position, i.e., at the para-position, thecontent of impurities increases since purification becomes difficult andthe properties of the obtained organic EL device deteriorate. By thesubstitution of aryl groups as described above, formation of pairs ofthe molecules by association is suppressed and the quantum efficiency offluorescence emission increases. Thus, the efficiency of light emissionof the organic EL device is improved.

In the compound represented by general formula [10] in the presentinvention, Ar¹ and Ar³ each independently represents a divalent groupselected from the group consisting of substituted and unsubstitutedphenylene groups, substituted and unsubstituted 1,3-naphthalene groups,substituted and unsubstituted 1,8-naphthalene groups, substituted andunsubstituted fluorene groups and substituted and unsubstituted biphenylgroups, Ar² represents a divalent group selected from the groupconsisting of substituted and unsubstituted anthracene nuclei,substituted and unsubstituted pyrene nuclei, substituted andunsubstituted phenanthrene nuclei, substituted and unsubstitutedchrysene nuclei, substituted and unsubstituted pentacene nuclei,substituted and unsubstituted naphthacene nuclei and substituted andunsubstituted fluorene nuclei. Examples of the divalent group include:

X⁵ to X⁸ and Y¹ to Y⁴ each independently represent the same groups asthose described in general formula [9]. a to d each represent an integerof 0 to 2, a+b+c+d≦2, e represents 0 or 1 and f represents 1 or 2,wherein, when Ar² represents an anthracene nucleus, the case in whicha=b=c=d and Ar¹ and Ar³ both represent p-phenylene group is excluded.

As described above, since the compound represented by general formula[10] in the present invention has a diamine structure, the ionizationenergy is 5.6 eV or smaller and holes can be easily injected. Themobility of holes is 10⁻⁴ m²/V·s or greater. Therefore, the compound hasthe excellent properties as the hole injecting material and the holetransporting material, in particular as the light emitting material. Dueto the polyphenyl structure of the compound having the condensed ring atthe center, electrons can be easily injected.

Since the compound has both of the polyphenyl structure and the diaminestructure, a stable amorphous thin film can be formed and exhibitsexcellent heat resistance due to the glass transition temperature of100° C. or higher. When the compound contains two or more structuresrepresented by general formula [2], the condition of a+b+c+d≦2 isrequired because the compound decomposes under heating in vapordeposition for formation of the thin film. When Ar² represents ananthracene nucleus, decomposition under heating and oxidation in vapordeposition can be prevented by the above specific structures of Ar¹ andAr³.

In the compounds represented by general formulae [11] and [11′] in thematerial for the organic EL devices and the novel compound used in theorganic EL device of the present invention, F represents a substitutedor unsubstituted arylene group having 6 to 21 carbon atoms. Examples ofthe group represented by F include divalent groups formed from biphenyl,terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene,thiophene and fluoranthene.

In general formulae [11] and [11′], a to d each represent an integer of0 to 2, wherein a+b+c+d>0.

As described above, since the compounds represented by general formulae[11] and [11′] in the present invention have a diamine structure at thecenter and a styrylamine structure at end portions, the ionizationenergy is 5.6 eV or smaller. Therefore, the property of injecting holesinto the light emitting layer is improved by adding the compound intothe light emitting layer. Moreover, the balance between electrons andholes in the light emitting layer is improved by catching holes and theefficiency of light emission and the life are improved. The efficiencyof light emission and the life are improved in comparison with the casein which the light emitting layer is composed of the above compoundrepresented by general formula [11] or [11′] alone as the sole materialfor the organic EL material

The compound having the structure in which X¹ and X² are bonded to eachother and X³ and X⁴ are bonded to each other through a single bond orthrough a carbon ring bond provides an elevated glass transitiontemperature and improved heat resistance.

In the group represented by general formulae [12] to [14] in the presentinvention, R^(5′) to R^(34′) each independently represent hydrogen atom,a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,a substituted or unsubstituted aryl group having 6 to 20 carbon atoms orcyano group and adjacent groups among the groups represented by R^(5′)to R^(24′) may be bonded to each other to form a saturated orunsaturated carbon ring. Examples of the group represented by R^(5′) toR^(34′) include substituted and unsubstituted alkyl groups such asmethyl group, ethyl group, propyl group, butyl group, sec-butyl group,tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group,stearyl group, 2-phenylisopropyl group, trichloromethyl group,trifluoromethyl group, benzyl group, α-phenoxybenzyl group,α,α-dimethylbenzyl group, α,α-methylphenylbenzyl group,α,α-ditrifluoromethylbenzyl group, triphenyl-methyl group andα-benzyloxybenzyl group; and substituted and unsubstituted aryl groupssuch as phenyl group, 2-methylphenyl group, 3-methylphenyl group,4-methylphenyl group, 4-ethylphenyl group, biphenyl group,4-methylbiphenyl group, 4-ethylbiphenyl group, 4-cyclohexyl-biphenylgroup, terphenyl group, 3,5-dichlorophenyl group, naphthyl group,5-methylnaphthyl group, anthryl group and pyrenyl group.

In the following, Compounds (1) to (28) as the typical examples of thecompound represented by general formula [1], Compounds (29) to (56) asthe typical examples of the compounds represented by general formulae[3] to [6], Compounds (57) to (74) as the typical examples of thecompound represented by general formula [7], Compounds (75) to (86) asthe typical examples of the compound represented by general formula [8],Compounds (87) to (104) as the typical examples of the compoundrepresented by general formula [9], Compounds (105) to (126) as thetypical examples of the compound represented by general formula [10] andCompounds (127) to (141) as the typical examples of the compoundsrepresented by general formulae [11] and [11′] are shown. However, thepresent invention is not limited to these typical examples.

The compounds represented by general formulae [1], [3] to [10] of thepresent invention exhibit strong fluorescence in the solid state, havethe excellent light emitting property in the electric field and show aquantum efficiency of fluorescence emission of 0.3 or greater since thepolyphenyl structure represented by A or B and the amine structure areconnected to each other at the center of the compounds. The compoundsrepresented by general formulae [7] and [8] exhibit strong fluorescencein the solid state or the dispersed state in the fluorescence region ofyellow color, orange color or red color and have an excellent lightemitting property in the electric field since the structure containingthe tetracene nucleus or the pentacene nucleus and the amine structureare connected to each other.

The compounds represented by general formulae [1], [3] to [10] of thepresent invention can be used effectively as the light emitting materialand may be used also as the hole transporting material, the electrontransporting material and the doping material since the compounds haveall of the hole injecting property from metal electrodes or organic thinfilm layers, the hole transporting property, the electron injectingproperty from metal electrodes or organic thin film layers and theelectron transporting property. In particular, when the compoundsrepresented by general formula [7] and [8] are used as the dopingmaterial, highly efficient emission of red light can be achieved sincethe compounds works as the center of recombination of electrons andholes.

The compound represented by general formula [8] exhibits a particularlyexcellent property since the arylamine and tetracene are bonded at thespecific positions.

The organic EL device of the present invention is a device in which oneor a plurality of organic thin films are disposed between an anode and acathode. When the device has a single layer, a light emitting layer isdisposed between an anode and a cathode. The light emitting layercontains a light emitting material and may also contain a hole injectingmaterial or a electron injecting material to transport holes injected atthe anode or electrons injected at the cathode to the light emittingmaterial. However, it is possible that the light emitting layer isformed with the light emitting material of the present invention alonebecause the light emitting material of the present invention has a veryhigh quantum efficiency of fluorescence emission, excellent ability totransfer holes and excellent ability to transfer electrons and a uniformthin film can be formed. The organic EL device of the present inventionhaving a multi-layer structure has a laminate structure such as: (ananode/a hole injecting layer/a light emitting layer/a cathode), (ananode/a light emitting layer/an electron injecting layer/a cathode) and(an anode/a hole injecting layer/a light emitting layer/an electroninjecting layer/a cathode). Since the compounds represented by generalformulae [1], [3] to [11], [11′] and [17] have the excellent lightemitting property and, moreover, the excellent hole injecting property,hole transporting property, electron injecting property and electrontransporting property, the compounds can be used for the light emittinglayer as the light emitting material.

In the light emitting layer, where necessary, conventional lightemitting materials, doping materials, hole injecting materials andelectron injecting materials may be used in addition to the compoundsrepresented by general formulae [1], [3] to [11], [11′] and [17] of thepresent invention. Deterioration in luminance and life caused byquenching can be prevented by the multi-layer structure of the organicEL. Where necessary, a light emitting materials, a doping materials, ahole injecting materials and an electron injecting materials may be usedin combination. By using a doping material, luminance and the efficiencyof light emission can be improved and blue light and red light can beemitted. The hole injecting layer, the light emitting layer and theelectron injecting layer may each have a multi-layer structure havingtwo or more layers. When the hole injecting layer has a multi-layerstructure, the layer into which holes are injected from the electrode isreferred to as the hole injecting layer and the layer which receivesholes from the hole injecting layer and transports holes from the holeinjecting layer to the light emitting layer is referred to as the holetransporting layer. When the electron injecting layer has a multi-layerstructure, the layer into which electrons are injected from theelectrode is referred to as the electron injecting layer and the layerwhich receives electrons from the electron injecting layer andtransports electrons from the electron injecting layer to the lightemitting layer is referred to as the electron transporting layer. Theselayers are each selected and used in accordance with factors such as theenergy level and heat resistance of the material and adhesion with theorganic layers or the metal electrodes.

Examples of the material which can be used in the light emitting layeras the light emitting material or the doping material in combinationwith the compounds represented by general formulae [1], [3] to [11],[11′] and [17] include anthracene, naphthalene, phenanthrene, pyrene,tetracene, coronene, chrysene, fluoresceine, perylene, phthaloperylene,naphthaloperylene, perynone, phthaloperynone, naphthaloperynone,diphenylbutadiene, tetraphenylbutadiene, coumarine, oxadiazole,aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, metalcomplexes of quinoline, metal complexes of aminoquinoline, metalcomplexes of benzoquinoline, imines, diphenylethylene, vinylanthracene,diamino-carbazole, pyrane, thiopyrane, polymethine, merocyanine, oxinoidcompounds chelated with imidazoles, quinacridone, rubrene, stilbenederivatives and fluorescent dyes. However, the examples of the abovematerial are not limited to the above compounds.

In particular, metal complexes of quinoline and stilbene derivatives canbe used in combination with the compounds represented by generalformulae [7] and [8] as the light emitting material or the dopingmaterial in the light emitting layer.

It is essential that the content of the doping material in the lightemitting layer is greater than the content of the compound representedby general formula [11] or [11′]. It is preferable that the content is80 to 99.9% by weight.

As the hole injecting material, a compound which has the ability totransfer holes, exhibits excellent effect of hole injection from theanode and excellent effect of hole injection to the light emitting layeror the light emitting material, prevents transfer of excited componentsformed in the light emitting layer into the electron injecting layer orthe electron injecting material and has an excellent ability to form athin film is preferable. Examples of such a compound includephthalocyanine derivatives, naphthalocyanine derivatives, porphyrinderivatives, oxaozole, oxadiazole, triazole, imidazole, imdazolone,imdazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole,oxadiazole, hydrazone, acylhydrazone, polyarylalkanes, stilbene,butadiene, benzidine-type triphenylamine, styrylamine typetriphenylamine, diamine type triphenylamine, derivatives of thesecompounds and macromolecular compounds such as polyvinylcarbazole,polysilane and conductive macromolecules. However, examples of such acompound are not limited to the compounds described above.

Among the hole injection materials which can be used in the organic ELdevice of the present invention, more effective hole injecting materialsare aromatic tertiary amine derivatives and phthalocyanine derivatives.

Examples of the aromatic tertiary amine derivative includetriphenylamine, tritolylamine, tolyldiphenylamine,N,N′-diphenyl-N,N′-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine,N,N,N′,N′-(4-methylphenyl) 1,1′-phenyl-4,4′-diamine,N,N,N′,N′-(4-methylphenyl)-1,1′-biphenyl-4,4′-diamine,N,N′-diphenyl-N,N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine,N,N′-(methylphenyl)-N,N′-(4-n-butylphenyl)phenanthrene-9,10-diamine,N,N-bis(4-di-4-tolylaminophenyl)-4-phenylcyclohexane and oligomers andpolymers having a skeleton structure of these aromatic tertiary amines.However, examples of the aromatic tertiary amine derivative are notlimited to the above compounds.

Examples of the phthalocyanine (Pc) derivative include H₂Pc, CuPc, CoPc,NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂SiPc,(HO)AlPc, (HO)GaPc, VOPc, TiOPc, MoOPc, GaPc-O—GaPc and correspondingderivatives of naphthalocyanine. However, examples of the derivatives ofphthalocyanine and naphthalocyanine are not limited to the abovecompounds.

As the electron injecting material, a compound which has the ability totransport electrons, exhibits excellent effect of electron injectionfrom the cathode and excellent effect of electron injecting to the lightemitting layer or the light emitting material, prevents transfer ofexcited components formed in the light emitting layer into the holeinjecting layer or the hole injecting material and has an excellentability to form a thin film is preferable. Examples of such a compoundinclude fluorenone, anthraquinodimethane, diphenoquinone, thiopyranedioxide, oxazole, oxadiazole, triazole, imidazole,peryleneteteracarboxylic acid, fluorenylidenemethane,anthraquinodimethane, anthrone and derivatives of these compounds.However, examples of such a compound is not limited to the compoundsdescribed above. The electron injecting property can be improved byadding an electron accepting material to the hole injecting material oran electron donating material to the electron injecting material.

In the organic EL device of the present invention, more effectiveelectron injecting materials are metal complex compounds andfive-membered derivatives containing nitrogen.

Examples of the metal complex compound include8-hydroxyquinolinatolithium, bis(8-hydroxyquinolinato)zinc,bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese,tris(8-hydroxyquinolinato)aluminum,tris(2-methyl-8-hydroxyquinolinato)-aluminum,tris(8-hydroxyquinilinato)gallium,bis(10-hydroxybenzo-[h]quinolinato)beryllium,bis(10-hydroxybenzo[h]quinolinato)zinc,bis(2-methyl-8-quinolinato)chlorogallium,bis(2-methyl-8-quinolinato)(o-cresolato)gallium,bis(2-methyl-8-quinolinato) (1-naphtholato)aluminum andbis(2-methyl-8-quinolinato)(2-naphtholato)gallium. However, examples ofthe metal complex compound are not limited to the above compounds.

Preferable examples of the five-membered derivative containing nitrogeninclude derivatives of oxazoles, thiazoles, thiadiazoles and triazoles.Specific examples include 2,5-bis(1-phenyl)-1,3,4-oxazole,dimethylPOPOP, 2,5-bis(1-phenyl)-1,3,4-thiazole,2,5-bis(1-phenyl)-1,3,4-oxadiazole,2-(4′-tert-butylphenyl)-5-(4″-biphenyl)-1,3,4-oxadiazole,2,5-bis(1-naphthyl)-1,3,4-oxadiazole,1,4-bis[2-(5-phenyloxadiazolyl)]benzene,1,4-bis[2-(5-phenyloxadiazolyl)-4-tert-butylbenzene],2-(4′-tert-butylphenyl)-5-(4″-biphenyl)-1,3,4-thiadiazole,2,5-bis(1-naphthyl)-1,3,4-thiadiazole,1,4-bis[2-(5-phenylthiadiazolyl)]benzene,2-(4′-tert-butylphenyl)-5-(4″-biphenyl)-1,3,4-triazole,2,5-bis(1-naphthyl)-1,3,4-triazole and1,4-bis[2-(5-phenyltriazolyl)]benzene. However, examples of thefive-membered derivative containing nitrogen are not limited to theabove compounds.

In the organic EL device of the present invention, at least one of lightemitting materials, doping materials, hole injecting materials andelectron injecting materials may be contained in the same layer of thelight emitting layer in addition to the compounds represented by generalformulae [1] and [3] to [8]. In order to improve stability of theorganic EL device of the present invention with respect to thetemperature, the humidity and the oxygen, a protecting layer may beformed on the entire surface of the device or the entire device may beprotected with silicon oil or a resin.

As the conductive material used as the anode of the organic EL device, amaterial having a work function of 4 eV or greater is suitable. Examplesof such a material include carbon, aluminum, vanadium, iron, cobalt,nickel, tungsten, silver, gold, platinum, palladium, alloys of thesemetals, metal oxides used for ITO substrates and NESA substrates such astin oxide and indium oxide and organic conductive resins such aspolythiophene and polypyrrol. As the conductive material used for thecathode, a material having a work function smaller than 4 eV issuitable. Examples of such a material include magnesium, calcium, tin,lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum andalloys of these metals. However, examples of the materials used for theanode and the cathode are not limited to the above examples. Typicalexamples of the alloy include alloys of magnesium and silver, alloys ofmagnesium and indium and alloys of lithium and aluminum. However,examples of the alloy are not limited to these alloys. The compositionof the alloy is determined by the temperature of the source of vapordeposition, the atmosphere and the degree of vacuum and a suitablecomposition is selected. The anode and the cathode may have amulti-layer structure having two or more layers, where necessary.

In the organic EL device, it is preferable that at least one face of thedevice is sufficiently transparent in the wave length region of emittedlight to achieve efficient light emission. It is preferable that thesubstrate is also transparent. In the preparation of the transparentelectrode, the above conductive material is used and vapor deposition orsputtering is conducted so that the prescribed transparency is surlyobtained. It is preferable that the electrode disposed on the lightemitting face has a light transmittance of 10% or greater. The substrateis not particularly limited as long as the substrate has mechanicalstrength and strength at high temperatures and is transparent. Glasssubstrates or transparent films of resins may be used. Example of thetransparent films of resins include films of polyethylene,ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers,polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride,polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketones,polsulfones, polyether sulfones, tetrafluoroethylene-perfluoroalkylvinyl ether copolymers, polyvinyl fluoride,tetrafluoro-ethylene-ethylene copolymers,tetrafluoroethylene-hexafluoropropylene copolymers,polychlorotrifluoroethylene, polyvinylidene fluoride, polyesters,polycarbonates, polyurethanes, polyimides, polyether imides, polyimidesand polypropylene.

Each layer of the organic EL device of the present invention can beproduced suitably in accordance with a dry process of film formationsuch as vacuum vapor deposition, sputtering and plasma and ion platingor a wet process of film formation such as spin coating, dipping andflow coating. The thickness of the film is not particularly limited.However, it is necessary that the thickness be set at a suitable value.When the thickness is greater than the suitable value, a great voltagemust be applied to obtain a prescribed output of light and theefficiency deteriorates. When the thickness is smaller than the suitablevalue, pin holes are formed and a sufficient luminance cannot beobtained even when the electric field is applied. In general, thesuitable range of the thickness is 5 nm to 10 μm. A thickness in therange of 10 nm to 0.2 μm is preferable.

When the device is produced in accordance with a wet process, materialsforming each layer are dissolved or dispersed in a suitable solvent suchas ethanol, chloroform, tetrahydrofuran and dioxane and a film is formedfrom the solution or the suspension. The solvent is not particularlylimited. In any organic thin layer, suitable resins and additives may beused to improve the property to form a film and to prevent formation ofpin holes. Examples of the resin which can be used include insulatingresins such as polystyrene, polycarbonates, polyarylates, polyesters,polyamides, polyurethanes, polysulfones, polymethyl methacrylate,polymethyl acrylate and cellulose, copolymers derived from these resins,photoconductive resins such as poly-N-vinylcarbazole and polysilane andconductive resins such as polythiophene and polypyrrol. Examples of theadditive include antioxidants, ultraviolet light absorbents andplasticizers.

As described above, by using the compounds of the present invention forthe light emitting layer of the organic EL device, practicallysufficient luminance can be obtained under application of a low voltage.Therefore, the organic EL device exhibiting a high efficiency of lightemission and having a long life due to suppressed degradation andexcellent heat resistance can be obtained.

The organic EL device of the present invention can be used for a planarlight emitting member such as a flat panel display of wall televisions,a back light for copiers, printers and liquid crystal displays, a lightsource of instruments, display panels and a marker light.

The materials of the present invention can be used not only for theorganic EL devices but also in the field of electronic photosensitivematerials, opto-electric conversion devices, solar batteries and imagesensors.

Examples of the primary amine represented by general formula [15] whichis used in the process for producing a material for organic EL devicesof the present invention include primary alkylamines such asmethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, n-amylamine,isoamylamine, tert-amylamine, cyclohexylamine, n-hexylamine,heptylamine, 2-aminoheptane, 3-aminoheptane, octylamine, nonylamine,decylamine, undecylamine, dodecylamine, tridecylamine,1-tetradecylamine, pentadecylamine, 1-hexadecylamine and octadecylamine;primary alkyldiamines such as ethylenediamine, 1,2-diaminopropane,1,3-diaminopropane and 1,4-diaminobutane; arylamines such as aniline,o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-toluidine,m-toluidine, p-toluidine, o-anisidine, m-anisidine, p-anisidine,1-naphthylamine, 2-naphthylamine, 1-aminoanthracene, 2-aminoanthracene,2-aminobiphenyl, 4-aminobiphenyl, 9-aminophenanthrene,2-trifluoromethyltoluidine, 3-trifluoromethyltoluidine and4-trifluoromethyltoluidine; aryldiamines such as o-phenylenediamine,m-phenylenediamine, p-phenylenediamine, fluorenediamine and1,8-naphthalenediamine; and the following compounds:

Examples of the secondary amine represented by general formula [15]include the following compounds:

The aryl halide represented by general formula [16] is not particularlylimited. The group represented by Ar is, in general, an alkyl grouphaving 1 to 18 carbon atoms or a substituted or unsubstituted aryl grouphaving 6 to 22 carbon atoms, The aromatic ring may have substituents. Inthe present invention, the aryl group include hydrocarbon groups havingcondensed rings.

Examples of the aryl halide include aryl bromides such as bromobenzene,o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromotoluene,o-bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol,p-bromophenol, 2-bromobenzotrifluoride, 3-bromobenzotrifluoride,4-bromobenzenetrifluoride, 1-bromo-2,4-dimethoxybenzene,1-bromo-2,5-dimethoxybenzene, 2-bromophenetyl alcohol, 3-bromophenetylalcohol, 4-bromophenetyl alcohol, 5-bromo-1,2,4-trimethylbenzene,2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene,4-bromo-m-xylene, 5-bromo-m-xylene, 1-bromo-3-(trifluoromethoxy)benzene,1-bromo-4-(trifluoromethoxy)benzene, 2-bromobiphenyl, 3-bromobiphenyl,4-bromobiphenyl, 4-bromo-1,2-(methylenedioxy)benzene,1-bromo-naphthalene, 2-bromonaphthalene, 1-bromo-2-methylnaphthalene and1-bromo-4-methylnaphthalene; aryl chlorides such as chlorobenzene,o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene,m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol,p-chlorophenol, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride,4-chlorobenzenetrifluoride, 1-chloro-2,4-dimethoxybenzene,1-chloro-2,5-dimethoxybenzene, 2-chlorophenetyl alcohol,3-chlorophenetyl alcohol, 4-chlorophenetyl alcohol,5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p-xylene,3-chloro-o-xylene, 4-chloro-o-xylene, 4-chloro-m-xylene,5-chloro-m-xylene, 1-chloro-3-(trifluoromethoxy)benzene,1-chloro-4-(trifluoromethoxy)benzene, 2-chlorobiphenyl,3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene,2-chloronaphthalene, 1-chloro-2-methylnaphthalene and1-chloro-4-methylnaphthalene; aryl iodides such as iodobenzene,o-iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene,m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol,2-iodobenzotrifluoride, 3-iodobenzotrifluoride,4-iodobenzenetrifluoride, 1-iodo-2,4-dimethoxybenzene,1-iodo-2,5-dimethoxybenzene, 2-iodophenetyl alcohol, 3-iodophenetylalcohol, 4-iodophenetyl alcohol, 5-iodo-1,2,4-trimethylbenzene,2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene,4-iodo-m-xylene, 5-iodo-m-xylene, 1-iodo-3-(trifluoromethoxy)benzene,1-iodo-4-(trifluoromethoxy)benzene, 2-iodobiphenyl, 3-iodobiphenyl,4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene,1-iodo-2-methylnaphthalene and 1-iodo-4-methylnaphthalene; arylfluorides such as fluorobenzene, o-fluoroanisole, m-fluoroanisole,p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p fluorotoluene,o-fluorophenol, m-fluorophenol, p-fluorophenol,2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride,4-fluorobenzenetrifluoride, 1-fluoro-2,4-dimethoxybenzene,1-fluoro-2,5-dimethoxybenzene, 2-fluorophenetyl alcohol,3-fluorophenetyl alcohol, 4-fluorophenetyl alcohol,5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene, 2-fluoro-p-xylene,3-fluoro-o-xylene, 4-fluoro-o-xylene, 4-fluoro-m-xylene,5-fluoro-m-xylene, 1-fluoro-3-(trifluoromethoxy)benzene,1-fluoro-4-(trifluoromethoxy)benzene, 2-fluorobiphenyl,3-fluorobiphenyl, 4-fluorobiphenyl,4-fluoro-1,2-(methylenedioxy)benzene, 1-fluoronaphthalene,2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene and1-fluoro-4-methylnaphthalene; and the following compounds:

Aryl halides having 2 or more halogen atoms and preferably 2 or 3halogen atoms can also be used as long as the object of the presentinvention is not adversely affected. Examples of the aryl halide having2 or more halogen atoms include 1,2-dibromobenzene, 1,3-dibromobenzene,1,4-dibromobenzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene,4,4′-dibromobiphenyl, 4,4′-dichlorobiphenyl, 4,4′-diiodobiphenyl,1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene,1-bromo-4-fluorobenzene, 2-bromochlorobenzene, 3-bromochlorobenzene,4-bromochlorobenzene, 2-bromo-5-chlorotoluene,3-bromo-4-chlorobenzotrifluoride, 5-bromo-2-chlorobenzotrifluoride,1-bromo-2,3-dichlorobenzene, 1-bromo-2,6-dichlorobenzene,1-bromo-3,5-dichlorobenzene, 2-bromo-4-fluorotoluene,2-bromo-5-fluorotoluene, 3-bromo-4-fluorotoluene,4-bromo-2-fluorotoluene, 4-bromo-3-fluorotoluene,tris(4-bromophenyl)amine, 1,3,5-tribromobenzene and the followingcompounds:

In the process for producing materials for organic EL devices of thepresent invention, the method of addition of the aryl halide is notparticularly limited. For example, two different types of aryl halidesmay be mixed with a primary amine before starting the reaction and thereaction may be conducted using the obtained mixture. Alternatively, aprimary amine may be reacted with one of two types of aryl halides.Then, the obtained secondary amine may be added to the other aryl halideand the reaction is conducted. The latter method in which different arylhalides are added successively is preferable because a tertiary aminecan be produced more selectively.

The amount of the added aryl halide is not particularly limited. Whenthe two types of aryl halides are added to the primary aminesimultaneously, it is suitable that the amount of the aryl halide is inthe range of 0.5 to 10 moles per 1 mole of the primary amine. From thestandpoint of economy and easier treatments after the reaction such asseparation of the unreacted aryl halide, it is preferable that theamount of the aryl halide is in the range of 0.7 to 5 moles per 1 moleof the primary amine. When the two types of aryl halides are addedsuccessively to the primary amine, the aryl halide which is added firstis added to the reaction system in an amount in the range of 0.5 to 1.5moles per 1 mole of the amino group in the primary amine. From thestandpoint of improving the selectivity of the tertiary amine of theobject compound, it is preferable that the above aryl halide is added tothe reaction system in an amount of 0.9 to 1.1 mole per 1 mole of theamino group in the primary amine.

The aryl halide which is added after preparation of the secondary amineis added in an amount of 0.1 to 10 mole per 1 mole of the amino group inthe primary amine used as the starting material. To prevent complicatedoperations in separation of the unreacted aryl halide and the unreactedsecondary amine after the reaction, it is preferable that the arylhalide is added in an amount of 0.9 to 5 mole per 1 mole of the aminogroup in the primary amine used as the starting material.

The palladium compound used as the catalyst component in the presentinvention is not particularly limited as long as it is a compound ofpalladium. Examples of the palladium compound include compounds oftetravalent palladium such as sodium hexachloropalladate(IV)tetrahydrate and potassium hexachloropalladate(IV); compounds ofdivalent palladium such as palladium(II) chloride, palladium(II)bromide, palladium(II) acetate, palladium acetylacetonate(II),dichlorobis-(benzonitrile)palladium(II),dichlorobis(acetonitrile)palladium(II),dichloro(bis(diphenylphosphino)ethane)palladium(II),dichlorobis-(triphenylphosphine)palladium(II),dichlorotetraamminepalladium(II),dichloro(cycloocta-1,5-diene)palladium(II) and palladiumtrifluoro-acetate(II); and compounds of zero-valent palladium such astris(dibenzylideneacetone) dipalladium(0) (Pd₂(dba)₃), chloroformcomplex of tris(dibenzylideneacetone) dipalladium(0), tetrakis(triphenylphosphine)palladium(0) and bis is(diphenylphosphino)ethane-palladium(0).In the process of the present invention, the amount of the palladiumcompound is not particularly limited. The amount of the palladiumcompound is 0.00001 to 20.0% by mole as the amount of palladium per 1mol of the primary amine. The tertiary amine can be synthesized with ahigh selectivity when the amount of the palladium compound is in theabove range. Since the palladium compound is expensive, it is preferablethat the amount of the palladium compound is 0.001 to 5.0 mole as theamount of palladium per 1 mole of the primary amine.

In the process of the present invention, the trialkylphosphine compoundused as the catalyst component is not particularly limited. Examples ofthe trialkylphosphine compound include triethylphosphine,tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine,triisobutylphosphine, tri-sec-butylphosphine andtri-tert-butylphosphine. Among these compounds, tri-tert-butylphosphineis preferable because of the high reaction activity. Thetriarylphosphine compound is not particularly limited. Examples of thetriarylphosphine include triphenylphosphine, benzyldiphenylphosphine,tri-o-toluylphosphine, tri-m-toluylphosphine and tri-p-toluylphosphine.Among these compounds, triphenylphosphine and tri-o-toluylphosphine arepreferable. The diphosphine compound is not particularly limited.Examples of the diphosphine compound includebis(dimethylphosphino)methane, bis(dimethylphosphino)ethane,bis(dicyclohexylphosphino)methane, bis(dicyclohexylphosphino)ethane,bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,1,4-bis(diphenylphosphino)butane, bis(diphenylphosphino)ferrocene,(R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl((R)-BINAP),(S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl-((S)-BINAP),2,2′-bis(diphenylphosphino)-1,1′-bisnaphthyl((±)-BINAP),2S,3S-bis(diphenylphosphino)butane((S,S)-CHIRAPHOS),2R,3R-bis(diphenylphosphino)butane((R,R)-CHIRAPHOS),2,3-bis(diphenyl-phosphino)butane(±)-CHIRAPHOS),(R)-2,2′-bis(di-p-toluylphosphino)-1,1-binaphthyl((R)-Tol-BINAP),(S)-2,2′-bis(di-p-toluylphosphino)-1,1′-binaphthyl((S)-Tol-BINAP),2,2′-bis(di-p-toluylphosphino)-1,1′-bisnaphthyl((±)-Tol-BINAP),4R,5R-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxorane((R,R)-DIOP),4S,5S-bis(diphenylphosphino-methyl)-2,2-dimethyl-1,3-dioxorane(S,S)-DIOP),4,5-bis(diphenyl-phosphinomethyl)-2,2-dimethyl-1,3-dixorane((O)-DIOP),N,N-dimethyl-(S)-[(R)-1′,2-bis(diphenylphosphino)ferrocenyl]ethylamine((S),(R)-BPPFA),N,N′-dimethyl-(R)-1-[(S)-1′,2-bis(diphenylphosphino)ferrocenyl]-ethylamine((R),(S)-BPPFA) andN,N′-dimethyl-1-[1′,2-bis(diphenyl-phosphino)ferrocenyl]ethylamine((±)-BPPFA).Among these compounds, bis(diphenylphosphino)ethane,1,3-bis(diphenylphosphino)propane, bis(diphenylphosphino)ferrocene andBINAPs are preferable. BINAPs may be either optically active compoundsor racemic compounds.

The amounts of the trialkylphosphine compound, the triphenylphosphinecompound and the diphosphine compound are 0.01 to 10,000 mole per 1 moleof the palladium compound. As long as the amounts are in this range, theselectivity of the arylamine does not change. However, it is preferablethat the amount is 0.1 to 10 mole per 1 mol of the palladium compoundsince the phosphine compounds are expensive.

In the process of the present invention, the palladium compound and thephosphine compound are the essential components of the catalyst. Thecombination of these components is added to the reaction system as thecatalyst. As the method of addition of the components, the twocomponents may be added to the reaction system separately or in the formof a complex which is prepared in advance.

The base which can be used in the present reaction is not particularlylimited and can be selected from inorganic bases such as sodiumcarbonate and potassium carbonate and alkali metal alkoxides and organicbases such as tertiary amines. Preferable examples of the base includealkali metal alkoxides such as sodium mothoxide, sodium ethoxide,potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodiumtert-butoxide, potassium tert-butoxide and cesium carbonate (Cs₂CO₃).The base may be added into the reaction field without any treatment.Alternatively, the base may be prepared from an alkali metal, ahydrogenated alkali metal or a alkali metal hydroxide and an alcohol atthe place of reaction and used in the reaction field.

The amount of the base is not particularly limited. It is preferablethat the amount is 0.5 mole or more per 1 mole of the halogen atom inthe two different types of aryl halides which are added to the reactionsystem. When the amount of the base is less than 0.5 mol, the activityof the reaction decreases and the yield of the arylamine decreases.Therefore, such an amount is not preferable. When the base is added in agreat excess amount, the yield of the arylamine does not change and, onthe other hand, treatments after the reaction become complicated.Therefore, it is more preferable that the amount is 1.0 mole or more andless than 5 mole per 1 mole of the halogen atom.

The reaction in the process of the present invention is conducted, ingeneral, in the presence of an inert solvent. The solvent is notparticularly limited as long as the solvent does not adversely affectthe reaction much. Examples of the solvent include aromatic hydrocarbonsolvents such as benzene, toluene and xylene, ether solvents such asdiethyl ether, tetrahydrofuran and dioxane, acetonitrile,dimethylformamide, dimethylsulfoxide and hexamethylphosphotriamide.Aromatic hydrocarbon solvents such as benzene, toluene and xylene arepreferable.

It is preferable that the process of the present invention is conductedunder the ordinary pressure in an atmosphere of an inert gas such asnitrogen and argon. The process can be conducted also under an addedpressure.

In the process of the present invention, the temperature of the reactioncan be selected in the range of 20 to 300° C. and preferably in therange of 50 to 200° C. The time of the reaction can be selected in therange of several minutes to 72 hours.

The process of the present invention in which the arylamine compound isobtained in the presence of the catalyst comprising the phosphinecompound and the palladium compound and the base is specificallydescribed in Synthesis Examples 12, 13, 14, 17 and 20.

The present invention will be described more specifically with referenceto examples in the following. However, the present invention is notlimited to the examples.

SYNTHESIS EXAMPLE 1 (COMPOUND (2))

Synthesis of Intermediate Compound A

In a 200 ml round bottom flask, 0.38 g (2.04 mmole) of4-bromobenzaldehyde and 0.98 g (4.29 mmole) of ethyl benzylphosphonatewere dissolved in 40 ml of dimethylsulfoxide. To this was added 0.5 g(4.49 mmole) of potassium t-butoxide in small portions at the roomtemperature and the resulting mixture was stirred for 18 hours. Thereaction mixture was poured into 500 ml of water, solid was filtered togive yellow solid (0.5 g).

In a 100 ml round bottom flask, the crystals obtained above, 2.0 g (12.0mmole) of potassium iodide and 1.14 g (6.0 mmole) of copper iodide weredissolved in 10 ml of hexamethylphosphoramide and the resulting mixturewas stirred under heating at 150° C. for 6 hours. After the reaction wascompleted, 10 ml of a 1 N aqueous hydrochloric acid was added to thereaction mixture and the organic layer was extracted with toluene. Afterthe extract was concentrated, the reaction product was purified byrecrystallizing from a mixture of diethyl ether and methanol and 0.28 g(the yield: 45%) of the following Intermediate Compound A was obtained:

(Intermediate Compound A)

Synthesis of Intermediate Compound B

In a 50 ml round bottom flask, 3 g (17.4 mmole) of p-bromoaniline wassuspended in 10 ml of a 6 N aqueous hydrochloric acid and cooled. To thecooled suspension, a solution prepared by dissolving 1.25 g (18.1 mmole)of sodium sulfite in 5.3 ml of water was slowly added dropwise at aninner temperature of 4° C. The resulting mixture was stirred at the sametemperature for 1 hour and an aqueous solution of a diazonium compoundwas obtained.

Separately, in a 100 ml round bottom flask, 0.3 g (1.7 mmole) ofanthracene was dissolved in 5 ml of acetone. To this was added asolution prepared by dissolving 0.46 g of copper(II) chloride dihydratein 5.7 ml of water and the mixture was cooled to 4° C. To the cooledmixture, the aqueous solution of a diazonium compound obtained above wasadded at the same temperature and the resulting mixture was stirred forover night at the room temperature. After the reaction was completed,precipitated crystals were filtered, washed with methanol and dried and0.2 g (the yield: 24%) of the following Intermediate Compound B wasobtained:

(Intermediate Compound B)

Synthesis of Compound (2)

In a 100 ml round bottom flask, 0.018 g (0.2 mmole) of aniline wasdissolved in 5 ml of methylene chloride. To this was added 0.05 g (0.5mmole) of acetic anhydride and the resulting mixture was stirred at theroom temperature for 1 hour. Then, the reaction solvent was removed bydistillation and an oily compound was obtained. To the oily compound,0.56 g (1.8 mmole) of Intermediate Compound A, 5 g of potassiumcarbonate, 0.3 g of copper powder and 20 ml of nitrobenzene were addedand the resulting mixture was stirred at 210° C. for 2 days. Then, thesolvent was removed by distillation and 10 ml of diethylene glycol and asolution prepared by dissolving 3 g of potassium hydroxide into 10 ml ofwater were added. The resulting mixture was stirred at 110° C. for onenight. After the reaction was completed, a mixture of ethyl acetate andwater was added to the reaction mixture and the organic layer wasseparated. After the solvent was removed by distillation, crude crystalswere obtained.

Subsequently, into a 100 ml round bottom flask, the crude crystalobtained above, 0.05 g (0.1 mmole) of Intermediate Compound 1B, 5 g ofpotassium carbonate, 0.3 g of copper powder and 20 ml of nitrobenzenewere placed and the mixture was stirred under heating at 220° C. for 2days. After the reaction was completed, precipitated crystals wereseparated by filtration, washed with methanol, dried and purified inaccordance with the column chromatography (silica gel,hexane/toluene=1/1) and 0.017 g of yellow powder was obtained. Thepowder was identified to be Compound (2) by the measurements inaccordance with NMR, IR and FD-MS (the field desorption massspectrometry) (the yield: 20%).

SYNTHESIS EXAMPLE 2 (COMPOUND (9))

Synthesis of Intermediate Compound C

In a 200 ml round bottom flask, 51.2 g (0.3 mole) of diphenylamine, 71.4g (0.3 mole) of 1,4-dibromobenzene, 34.6 g (0.36 mole) of potassiumt-butoxide, 4.2 g (5.9 mmole) of PdCl₂(PPh₃)₂ and 1.2 liter of xylenewere mixed together and the obtained mixture was stirred at 130° C. forone night.

After the reaction was completed, the organic layer was concentrated andabout 100 g of brown crystals were obtained. The crystals were purifiedin accordance with the column chromatography (silica gel,hexane/toluene=10/1) and 28 g (the yield: 29%) of the followingIntermediate Compound C was obtained:

(Intermediate Compound C)

Synthesis of Compound (9)

In a 100 ml round bottom flask, 0.48 g (1 mmole) of IntermediateCompound B was dissolved in 10 ml of diethyl ether and the mixture wascooled to −78° C. To the cooled mixture, 2 ml (1.5 M, 3 mmole) ofn-butyllithium was added and the resulting mixture was stirred for 1hour. Then, a solution prepared by dissolving 0.3 g (3 mmole) oftrimethyl borate in 5 ml of diethyl ether was added dropwise to themixture. After the addition was completed, the resulting mixture wasstirred at −78° C. for 1 hour. Then, 10 ml of a 1 N aqueous hydrochloricacid was added at the room temperature. After the organic layer wasseparated, the solvent was removed by distillation and crude crystalswere obtained.

In a 100 ml round bottom flask, the crude crystals obtained above, 0.97g (3 mmole) of Intermediate Compound C, 12 mg of Pd(PPh₃)₄ and 0.32 g(1.5 mmole) of potassium phosphate were dissolved in 10 ml ofdimethylformamide and the resulting mixture was stirred at 100° C. for 4hours. After the organic layer was separated, the solvent was removed bydistillation and crude crystals were obtained. The crude crystals werepurified by the column chromatography (silica gel, benzene/ethylacetate=50/1) to give 0.13 g of yellow powder. The powder was identifiedto be Compound (9) by the measurements in accordance with NMR, IR andFD-MS (the yield: 14%).

SYNTHESIS EXAMPLE 3 (COMPOUND (18))

Synthesis of Intermediate Compound D

A Grignard reagent was prepared by adding magnesium and diethyl ether to0.48 g (2.0 mmol) of 1,4-dibromobenzene. Separately, in a 100 ml roundbottom flask, 5.7 g (20.0 mmole) of 1,4-dibromonaphthalene and 10 mg ofNiCl₂(dppp) were dissolved in 20 ml of diethyl ether and the resultingmixture was cooled in an ice bath. To the cooled mixture, the Grignardreagent prepared above was added and the obtained mixture was stirredunder refluxing for 6 hours. After the reaction was completed, 10 ml ofa 1 N aqueous hydrochloric acid was added. After the organic layer wasseparated, the solvent was removed by distillation and 0.30 (the yield:30%) of the following Intermediate Compound D was obtained:

(Intermediate Compound D)

Synthesis of Compound (18)

In a 100 ml round bottom flask, 0.09 g (1.0 mmole) of aniline and 0.25 g(2.5 mmole) of acetic anhydride were dissolved into 5 ml of methylenechloride. The resulting mixture was stirred at the room temperature for1 hour. Then, the solvent was removed by distillation and an oilycompound was obtained. To this was added 0.4 g (4.5 mmole) ofIntermediate Compound A, 5 g of potassium carbonate, 0.3 g of copperpowder and 20 ml of nitrobenzene and the resulting mixture was stirredunder heating at 210° C. for 2 days. Then, the solvent was removed bydistillation and 10 ml of diethylene glycol and a solution prepared bydissolving 3 g of potassium hydroxide into 10 ml of water were added tothe residue. The resulting mixture was stirred at 110° C. for one night.After the reaction was completed, a mixture of ethyl acetate and waterwas added to the reaction mixture. After the organic layer wasseparated, the solvent was removed and crude crystals were obtained.

Subsequently, into a 100 ml round bottom flask, the above crudecrystals, 0.5 g (1.0 mmole) of Intermediate Compound D, 5 g of potassiumcarbonate and 0.3 g of copper powder were dissolved in 20 ml ofnitrobenzene and the resulting mixture was stirred under heating at 220°C. for 2 days. After the reaction was completed, precipitated crystalswere filtered, washed with methanol, dried and purified by the columnchromatography (silica gel, hexane/toluene=1/1) to give 0.1 g of yellowpowder. The powder was identified to be Compound (18) by themeasurements in accordance with NMR, IR and FD-MS (the yield: 10%).

EXAMPLE 1

A cleaned glass plate having an ITO electrode was coated with acomposition which contained Compound (2) obtained above as the lightemitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole and apolycarbonate resin (manufactured by TEIJIN KASEI Co., Ltd.; PANLITEK-1300) in amounts such that the ratio by weight was 5:3:2 and wasdissolved in tetrahydrofuran in accordance with the spin coating and alight emitting layer having a thickness of 100 nm was obtained. On theobtained light emitting layer, an electrode having a thickness of 150 nmwas formed with an alloy prepared by mixing aluminum and lithium inamounts such that the content of lithium was 3% by weight and an organicEL device was obtained. The organic EL device exhibited a luminance ofemitted light of 200 (cd/m²), the maximum luminance of 14,000 (cd/m²)and an efficiency of light emission of 2.1 (lm/W) under application of adirect current voltage of 5 V.

EXAMPLE 2

On a cleaned glass plate having an ITO electrode, Compound (9) obtainedabove was vacuum vapor deposited as the light emitting material and alight emitting layer having a thickness of 100 nm was formed. On thelayer formed above, an electrode having a thickness of 100 nm was formedwith an alloy prepared by mixing aluminum and lithium in amounts suchthat the content of lithium was 3% by weight and an organic EL devicewas obtained. The light emitting layer was formed by vapor depositionunder a vacuum of 10⁻⁶ Torr while the temperature of the substrate waskept at the room temperature. The organic EL device exhibited aluminance of emitted light of about 110 (cd/m²), the maximum luminanceof 20,000 (cd/m²) and an efficiency of light emission of 2.1 (lm/W)under application of a direct current voltage of 5 V.

EXAMPLE 3

On a cleaned glass plate having an ITO electrode, Compound (2) obtainedabove was vacuum vapor deposited as the light emitting material and alight emitting layer having a thickness of 50 nm was formed. Then, anelectron injecting layer having a thickness of 10 nm was formed by vapordeposition of the following compound (Alq):

On the layer formed above, an electrode having a thickness of 100 nm wasformed with an alloy prepared by mixing aluminum and lithium in amountssuch that the content of lithium was 3% by weight and an organic ELdevice was obtained. The light emitting layer and the electron injectinglayer were formed by vapor deposition under a vacuum of 10⁻⁶ Torr whilethe temperature of the substrate was kept at the room temperature. Theorganic EL device emitted bluish green light with a luminance of emittedlight of about 600 (cd/m²), the maximum luminance of 30,000 (cd/m²) andan efficiency of light emission of 3.0 (lm/W) under application of adirect current voltage of 5 V. When the organic EL device was driven bya constant electric current at an initial luminance of emitted light of600 (cd/m²), the half life time was as long as 2,000 hours.

EXAMPLES 4 TO 16

On a cleaned glass plate having an ITO electrode, the light emittingmaterial shown in Table 1 was vapor deposited and a light emitting layerhaving a thickness of 80 nm was obtained. Then, the compound (Alq)described above was vacuum vapor deposited as the electron injectingmaterial and an electron injecting layer having a thickness of 20 nm wasformed. On the layer formed above, an electrode having a thickness of150 nm was formed with an alloy prepared by mixing aluminum and lithiumin amounts such that the content of lithium was 3% by weight. Organic ELdevices were obtained in this manner. The above layers were formed byvapor deposition under a vacuum of 10⁻⁶ Torr while the temperature ofthe substrate was kept at the room temperature. The light emittingproperties of the obtained devices are shown in Table 1. The organic ELdevices in these Examples all showed excellent luminances such as themaximum luminance of 10,000 (cd/m²) or greater. TABLE 1 Efficiency ofExample Type of light light emission Half life time No. emittingmaterial (lm/W) (hour) 4  (3) 2.8 3200 5  (4) 2.4 2600 6  (5) 3.0 3200 7 (6) 1.2 1200 8  (9) 2.8 2800 9 (10) 1.7 1700 10 (13) 1.0 1400 11 (14)2.1 2700 12 (15) 2.9 4200 13 (18) 1.6 1300 14 (20) 2.6 1800 15 (26) 3.14000 16 (27) 1.4 2100

EXAMPLE 17

On a cleaned glass plate having an ITO electrode, the following compound(TPD74):

was vacuum vapor deposited as the hole injecting material and a filmhaving a thickness of 60 nm was formed. Then, the following compound(NPD):

was vacuum vapor deposited on the film formed above as the holetransporting material and a film having a thickness of 20 nm was formed.Then, 4,4′-bis(2,2-diphenylvinyl)biphenyl (DPVBi) and Compound (3)obtained above were vapor deposited simultaneously and a layer having acontent of Compound (3) of 5% by weight and the thickness of 40 nm wasformed. Compound (3) works as the fluorescent dopant. Subsequently, thecompound (Alq) was vapor deposited as the electron injecting materialand a layer having a thickness of 20 nm was formed. Then, LiF was vapordeposited and a layer having a thickness of 0.5 nm was formed. Anelectrode was formed on the above layers by vapor deposition of aluminumand a layer having a thickness of 100 nm was formed. Thus, an organic ELwas obtained. The above layers were formed by vapor deposition under avacuum of 10⁻⁶ Torr while the temperature of the substrate was kept atthe room temperature. The organic EL device exhibited a luminance ofemitted light as high as about 750 (cd/m²) under application of a directcurrent voltage of 5 V. When the organic EL device was driven by aconstant electric current at an initial luminance of emitted light of400 (cd/m²), the half life time was as long as 3,000 hours.

COMPARATIVE EXAMPLE 1

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 1 except that the following Compound ofComparative Example 1:

(Compound of Comparative Example 1)

was used as the light emitting material. The obtained organic EL deviceexhibited a luminance of emitted light of 60 (cd/m²) and an efficiencyof light emission of 0.34 (lm/W) under application of a direct currentvoltage of 5 V. Sufficient properties could not be obtained.

COMPARATIVE EXAMPLE 2

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 3 except that the following Compound ofComparative Example 2:

(Compound of Comparative Example 2)

was used as the light emitting material. The obtained organic EL deviceexhibited a luminance of emitted light of 200 (cd/m²) and an efficiencyof light emission of 1.2 (lm/W) under application of a direct currentvoltage of 5 V. However, when the organic EL device was driven by aconstant electric current at an initial luminance of emitted light of400 (cd/m²), the half life time was as short as 600 hours.

Test of Heat Resistance

The organic EL devices prepared in Examples 2 and 3 and ComparativeExamples 1 and 2, which had been used for the measurement of luminanceof emitted light, were placed in a chamber kept at the constanttemperature of 100° C. After 500 hours, luminance of light emission wasmeasured again. The values of luminance before and after the deviceswere kept in the chamber were compared and the retention of luminancewas calculated.

The retentions of luminance of the organic EL devices prepared inExamples 2 and 3 and Comparative Examples 1 and 2 thus obtained were85%, 90%, 25% and 30%, respectively. As shown by this result, thecompounds used as the light emitting material in Comparative Examples 1and 2 could not retain luminance because the compounds had glasstransition temperatures lower than 100° C. In contrast, the compoundsused as the light emitting material in Examples 2 and 3 exhibitedexcellent heat resistance and could retain luminance for a long timebecause the compounds had glass transition temperatures higher than 110°C.

SYNTHESIS EXAMPLE 4 (COMPOUND (30))

Synthesis of Intermediate Compound E (6,12-diiodochrysene)

In a 300 ml round bottom flask, 5 g (22 mmole) of chrysene was dissolvedin 100 ml of carbon tetrachloride. To this was added 16 g (64 mmole) ofiodine dissolved in 100 ml of carbon tetrachloride dropwise at the roomtemperature. The resulting mixture was stirred under heating for 5hours, precipitated crystals were separated by filtration and thecrystals were washed with 100 ml of carbon tetrachloride. The crudecrystals were recrystallized from 200 ml of toluene and IntermediateCompound E was obtained (the yield: 35%).

Synthesis of Compound (30)

In a 100 ml two-necked flask, 2 g (10 mmole) of 4-aminostilbene wasdissolved in 20 ml of methylene chloride. To this was added 2.5 g (25mmole) of acetic anhydride. The resulting mixture was stirred at theroom temperature for 1 hour. Then, the reaction solvent was removed bydistillation and an oily compound was obtained. In a 300 ml two-neckedflask, 4.1 g (20 mmole) of iodobenzene, 3 g (30 mmole) of potassiumcarbonate, 0.06 g (1 mmole) of copper powder and 100 ml of nitrobenzenewere added to the obtained oily compound and the obtained mixture wasstirred under heating at 220° C. for 2 days. Then, the solvent wasremoved by distillation and 10 ml of diethylene glycol and a solutionprepared by dissolving 30 g of potassium hydroxide into 100 ml of waterwere added to the residue. The reaction was allowed to proceed at 110°C. for one night. After the reaction was completed, a mixture of ethylacetate and water was added to the reaction mixture. After the organiclayer was separated, the solvent was removed by distillation and crudecrystals were obtained.

Subsequently, in a 300 ml two-necked flask, the above crude crystals,2.4 g (5 mmole) of Intermediate Compound E, 3 g (20 mmole) of potassiumcarbonate and 0.06 g (1 mmole) of copper powder were dissolved in 100 mlof nitrobenzene and the resulting mixture was stirred under heating at230° C. for 2 days. After the reaction was completed, precipitatedcrystals were separated by filtration, washed with methanol, dried andpurified in accordance with the column chromatography (silica gel,hexane/toluene=1/1) and 1.0 g of yellow powder was obtained. The powderwas identified to be Compound (30) by the measurements in accordancewith NMR, IR and FD-MS (the yield: 25%).

SYNTHESIS EXAMPLE 5 (COMPOUND (36))

Synthesis of Compound (36)

In a 100 ml round bottom flask, 3.4 g (20 mmole) of diphenylamine, 4.8 g(10 mmole) of Intermediate Compound E, 3 g (30 mmole) of potassiumcarbonate and 0.06 g (1 mmole) of copper powder were dissolved in 100 mlof nitrobenzene and the resulting mixture was stirred under heating at210° C. for 2 days. After the reaction was completed, precipitatedcrystals were separated by filtration, washed with methanol, dried andpurified in accordance with the column chromatography (silica gel,hexane/toluene=1/1) and 2.8 g of yellow powder was obtained. The powderwas identified to be Compound (36) by the measurements in accordancewith NMR, IR and FD-MS (the yield: 50%).

SYNTHESIS EXAMPLE 6 (COMPOUND (38))

Synthesis of Compound (38)

In a 100 ml four-necked flask, 1.0 g (41 mmole) of magnesium, 1 ml oftetrahydrofuran and a small piece of iodine were placed under an argonstream. To this mixture, 9.7 g (30 mmole) of 4-bromotriphenylaminedissolved in 100 ml of tetrahydrofuran was slowly added dropwise at theroom temperature. After the addition was completed, the reaction mixturewas stirred under heating at 60° C. for 1 hour and a Grignard reagentwas prepared.

In a 300 ml four-necked flask, 4.8 g (10 mmole) of Intermediate CompoundE, 0.28 g (0.4 mmole) of PdCl₂(PPh₃)₂ and 1.0 ml (1 mmole) of a 1.0 Mtoluene solution of AlH(iso-Bu)₂ were dissolved in 50 ml oftetrahydrofuran under an argon stream. To this was added the Grignardreagent prepared above dropwise at the room temperature. The temperaturewas elevated and the reaction mixture was heated under refluxing forover night. After the reaction was completed, the reaction liquid wascooled with ice water. Precipitated crystals were separated byfiltration and washed with acetone. The obtained crude crystals wererecrystallized from 100 ml of acetone and 4.3 g of yellow powder wasobtained. The powder was identified to be Compound (38) by themeasurement in accordance with NMR, IR and FD-MS (the yield: 60%).

SYNTHESIS EXAMPLE 7 (COMPOUND (47))

Synthesis of Compound (47)

In a 100 ml two-necked flask, 2.4 g (10 mmole) of 6-aminochrysene wasdissolved into 20 ml of methylene chloride. To this was added 2.5 g (25mmole) of acetic anhydride and the resulting mixture was stirred at theroom temperature for 1 hour. Then, the reaction solvent was removed bydistillation and an oily compound was obtained. In a 300 ml two-neckedflask, 4.1 g (20 mmole) of iodobenzene, 3 g (30 mmole) of potassiumcarbonate and 0.06 g (1 mmole) of copper powder were dissolved in 100 mlof nitrobenzene. To this was added the oily compound and the resultingmixture was stirred under heating at 220° C. for 2 days. Then, thesolvent was removed by distillation and 10 ml of diethylene glycol and asolution prepared by dissolving 30 g of potassium hydroxide into 100 mlof water were added to the residue. The reaction was allowed to proceedat 110° C. for one night. After the reaction was completed, a mixture ofethyl acetate and water was added to the reaction mixture. After theorganic layer was separated, the solvent was removed by distillation andcrude crystals were obtained.

Subsequently, in a 300 ml two-necked flask, the crude crystals obtainedabove, 2 g (5 mmole) of 4,4′-diiodobiphenyl, 3 g (30 mmole) of potassiumcarbonate and 0.06 g (1 mmole) of copper powder were dissolved in 100 mlof nitrobenzene and the resulting mixture was stirred under heating at230° C. for 2 days. After the reaction was completed, precipitatedcrystals were separated by filtration, washed with methanol, dried andpurified in accordance with the column chromatography (silica gel,hexane/toluene=1/3) and 0.8 g of yellow powder was obtained. The powderwas identified to be Compound (47) by the measurements in accordancewith NMR, IR and FD-MS (the yield: 30%).

EXAMPLE 18

A cleaned glass plate having an ITO electrode was coated with acomposition which contained Compound (30) obtained above as the lightemitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole and apolycarbonate resin (manufactured by TEIJIN KASEI Co., Ltd.; PANLITEK-1300) in amounts such that the ratio by weight was 5:3:2 and wasdissolved in tetrahydrofuran in accordance with the spin coating and alight emitting layer having a thickness of 100 nm was obtained. On theobtained light emitting layer, an electrode having a thickness of 150 nmwas formed with an alloy prepared by mixing aluminum and lithium inamounts such that the content of lithium was 3% by weight and an organicEL device was obtained. The organic EL device exhibited a luminance ofemitted light of 320 (cd/m²), the maximum luminance of 14,000 (cd/m²)and an efficiency of light emission of 2.5 (lm/W) under application of adirect current voltage of 5 V.

EXAMPLE 19

On a cleaned glass plate having an ITO electrode, Compound (37) obtainedabove was vacuum vapor deposited as the light emitting material and alight emitting layer having a thickness of 100 nm was formed. On thelayer formed above, an inorganic electron injecting layer having athickness of the film of 0.3 nm was formed with lithium fluoride. Then,an electrode having a thickness of 100 nm was formed with aluminum andan organic EL device was obtained. The light emitting layer was formedby vapor deposition under a vacuum of 10⁻⁶ Torr while the temperature ofthe substrate was kept at the room temperature. The organic EL deviceexhibited a luminance of emitted light of about 110 (cd/m²), the maximumluminance of 20,000 (cd/m²) and an efficiency of light emission of 1.2(lm/W) under application of a direct current voltage of 5 V.

EXAMPLE 20

On a cleaned glass plate having an ITO electrode, CuPc was vacuum vapordeposited as the hole injecting material and a hole injecting layerhaving a thickness of 40 nm was formed. Then, a hole transporting layerhaving a thickness of 20 nm was formed by using Compound (47) obtainedabove as the hole transporting material and a light emitting layerhaving a thickness of 60 nm was formed by vacuum vapor deposition of thecompound (Alq) described above. Rubrene was added to the light emittinglayer in an amount of 4% by weight. On the layers formed above, anelectrode having a thickness of 100 nm was formed with an alloy preparedby mixing aluminum and lithium in amounts such that the content oflithium was 3% by weight and an organic EL device was obtained. Theabove layers were formed by vapor deposition under a vacuum of 10⁻⁶ Torrwhile the temperature of the substrate was kept at the room temperature.The organic EL emitted green light with a luminance of emitted light ofabout 700 (cd/m²), the maximum luminance of 80,000 (cd/m²) and anefficiency of light emission of 6.0 (lm/W) under application of a directcurrent voltage of 5 V. When the organic EL device was driven by aconstant electric current at an initial luminance of emitted light of600 (cd/m²), the half life time was as long as 4,000 hours.

EXAMPLES 21 TO 33

On a cleaned glass plate having an ITO electrode, a hole injecting layerhaving a thickness of 20 nm was formed by vacuum vapor deposition of thehole injecting material shown in Table 2. A light emitting layer havinga thickness of 60 nm was formed by vapor deposition of the compound(Alq) described above as the light emitting material and rubrene wasadded to the light emitting layer in an amount of 4% by weight. On thelayers formed above, an electrode having a thickness of 150 nm wasformed with an alloy prepared by mixing aluminum and lithium in amountssuch that the content of lithium was 3% by weight. Organic EL deviceswere obtained in this manner. The above layers were formed by vapordeposition under a vacuum of 10⁻⁶ Torr while the temperature of thesubstrate was kept at the room temperature. The light emittingproperties of the obtained devices are shown in Table 2. The organic ELdevices in these Examples all showed excellent luminances such as themaximum luminance of 10,000 (cd/m²) or greater. TABLE 2 Type of holeHalf life time Example transporting material (hour) ✓ 21 (30) 5200 ✓ 22(36) 5600 23 (37) 4200 24 (38) 3200 25 (41) 4800 26 (43) 6700 27 (48)2400 ✓ 28 (49) 5700 ✓ 29 (50) 5200 ✓ 30 (51) 6000 31 (53) 4000 32 (55)4000 33 (56) 3200

EXAMPLE 34

On a cleaned glass plate having an ITO electrode, compound (TPD74)described above was vacuum vapor deposited as the hole injectingmaterial and a layer having a thickness of 60 nm was formed. Then, thecompound (NPD) obtained above was vacuum vapor deposited as the holetransporting material and a layer having a thickness of 20 nm wasformed.

4,4′-bis(2,2-Diphenylvinyl)phenylanthracene (DPVDPAN) as the lightemitting material and Compound (36) described above as the dopant werevapor deposited simultaneously and a layer which had a content ofCompound (36) of 2% by weight and a thickness of 40 nm was formed. Then,the compound (Alq) described above was vapor deposited as the chargeinjecting material and a layer having a thickness of 20 nm was formed.After lithium fluoride was vapor deposited and a layer having athickness of 0.5 nm was formed, aluminum was vapor deposited and anelectrode having a thickness was 100 nm formed. Thus, an organic ELdevice was obtained. The above layers were formed by vapor depositionunder a vacuum of 10⁻⁶ Torr while the temperature of the substrate waskept at the room temperature. The organic EL device exhibited aluminance of emitted light as high as 500 (cd/m²) under application of adirect current voltage of 8 V and the emitted light had blue color ofexcellent purity. When the organic EL device was driven by a constantelectric current at an initial luminance of emitted light of 100(cd/m²), the half life time was as long as 7,000 hours.

The spectrum of the light emitted by this device was measured and it wasfound that the spectrum was the same as that of the device using DPVBi.This means that Compound (36) did not affect the light emission butexhibited the effect of extending the life of the device.

COMPARATIVE EXAMPLE 3

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 34 except that Compound (36) describedabove was not added as the dopant. When the prepared organic EL devicewas driven by a constant electric current at an initial luminance ofemitted light of 100 (cd/m²), the half life time was shorter than thehalf life time in Example 34, i.e., 4,000 hours.

COMPARATIVE EXAMPLE 4

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 20 except that Compound of ComparativeExample 2 described above was used as the hole transporting material.

The prepared organic EL device exhibited a luminance of emitted light of300 (cd/m²) and an efficiency of light emission of 4.2 (lm/W) underapplication of a direct current voltage of 5 V. However, when theorganic EL device was driven by a constant electric current at aninitial luminance of emitted light of 400 (cd/m²), the half life timewas as short as 300 hours.

Test of Heat Resistance

The organic EL devices prepared in Examples 20 and 27 and ComparativeExample 4, which had been used for the measurement of luminance ofemitted light, were placed in a chamber kept at the constant temperatureof 105° C. After 500 hours, luminance of light emission was measuredagain. The values of luminance before and after the devices were kept inthe chamber were compared and the retention of luminance was calculated.

The retentions of luminance of the organic EL devices prepared inExamples 20 and 27 and Comparative Example 4 thus obtained were 87%, 90%and 25%, respectively. As shown by this result, the compounds used asthe light emitting material in Comparative Example 4 could not retainluminance because the compounds had a glass transition temperature lowerthan 105° C. In contrast, the compounds used for the light emittingmaterial in Examples 20 and 27 exhibited excellent heat resistance andcould retain luminance for a long time because the compounds had glasstransition temperatures higher than 110° C.

SYNTHESIS EXAMPLE 8 (COMPOUND (58))

Synthesis of Intermediate Compound F (5,11-dibromonaphthacene)

In a 2 liter round bottom flask, 50 g (0.19 mmole) of 5,12-naphthacene,108 g (0.57 mmole) of tin(IV) chloride, 500 ml of acetic acid and 200 mlof concentrated hydrochloric acid were placed. The resulting mixture wasstirred for reflux for 2 hours. After the reaction was completed,precipitated crystals were separated by filtration, washed with waterand dried in a vacuum drying chamber and 48 g of crude crystals wereobtained.

Subsequently, in a 2 liter four-necked flask, the crude crystalsobtained above and 50 g (0.19 mmole) of triphenylphosphine weredissolved in 300 ml of dimethylformamide under an argon stream. To thiswas added 64 g (0.4 mmole) of bromine dissolved in 200 ml ofdimethylformamide slowly dropwise and the resulting mixture was stirredat ambient temperature. After the addition was completed, the mixturewas stirred under heating at 200° C. for one night. After the reactionwas completed, dimethylformamide was removed by distillation in vacuoand 200 ml of water was added to the residue. The organic layer wasextracted with toluene. The extract was dried with magnesium sulfate andconcentrated in vacuo using a rotary evaporator and an oily compound wasobtained. The oily compound was purified in accordance with the columnchromatography (silica gel, hexane/toluene=1/1) and 30 g of yellowpowder was obtained. The powder was identified to be IntermediateCompound F by the measurements in accordance with NMR, IR and FD-MS (theyield: 40%).

Synthesis of Compound (58)

In a 100 ml two-necked flask, 2 g (10 mmole) of 4-aminostilbene wasdissolved in 20 ml of methylene chloride. To this was added 2.5 g (25mmole) of acetic anhydride and the resulting mixture was stirred at theroom temperature for 1 hour. Then, the reaction solvent was removed bydistillation and an oily compound was obtained. In a 300 ml two-neckedflask, 4.1 g (20 mmole) of iodobenzene, 3 g (30 mmole) of potassiumcarbonate, 0.06 g (1 mmole) of copper powder and 100 ml of nitrobenzenewere added to the obtained oily compound and the obtained mixture wasstirred under heating at 220° C. for 2 days. Then, the solvent wasremoved by distillation and 10 ml of diethylene glycol and a solutionprepared by dissolving 30 g of potassium hydroxide into 100 ml of waterwere added to the residue. The reaction was allowed to proceed at 110°C. for one night. After the reaction was completed, a mixture of ethylacetate and water was added to the reaction mixture. After the organiclayer was separated, the solvent was removed and crude crystals wereobtained.

Subsequently, in a 100 ml two-necked flask, the crude crystals obtainedabove, 1.9 g (5 mmole) of Intermediate Compound F, 1.3 g (12 mmole) ofpotassium t-butoxide and 40 mg (5% by mole) of PdCl₂(PPh₃)₂ weredissolved in 30 ml of xylene under an argon stream. The resultingmixture was stirred under heating at 130° C. for over night. After thereaction was completed, precipitated crystals were separated byfiltration, washed with methanol, dried and purified in accordance withthe column chromatography (silica gel, hexane/toluene=1/1) and 0.9 g ofyellow powder was obtained. The powder was identified to be Compound(58) by the measurements in accordance with NMR, IR and FD-MS (theyield: 25%).

SYNTHESIS EXAMPLE 9

Synthesis of Compound (59)

In a 300 ml four-necked flask, 2 g (10 mmole) of 4-hydroxystilbene and5.2 g (20 mmole) of triphenylphosphine were dissolved in 50 ml ofdimethylformamide under an argon stream. To this mixture was added 5 g(20 mmole) of iodine dissolved in 50 ml of dimethylformamide slowlydropwise at the room temperature and the reaction was allowed toproceed. After the addition was completed, the reaction mixture wasstirred at 200° C. for over night. After the reaction was completed,dimethylformamide was removed by distillation in vacuo and 200 ml ofwater was added to the residue. The organic layer was extracted withtoluene. The extract was dried with magnesium sulfate and concentratedin vacuo using a rotary evaporator and an oily compound was obtained.The oily compound was purified in accordance with the columnchromatography (silica gel, hexane/toluene=1/1) and 2.5 g of yellowpowder was obtained.

Separately, in a 100 ml two-necked flask, 2 g (10 mmole) of4-aminostilbene was dissolved in 20 ml of methylene chloride. To thiswas added 2.5 g (25 mmole) of acetic anhydride and the resulting mixturewas stirred at the room temperature for 1 hour. Then, the reactionsolvent was removed by distillation and an oily compound was obtained.

In a 300 ml two-necked flask, 2.5 g of the yellow powder obtained above,3 g (30 mmole) of potassium carbonate, 0.06 g (1 mmole) of copper powderand 100 ml of nitrobenzene were added to the above oily compound. Theresulting mixture was stirred under heating at 220° C. for 2 days. Tothe residue obtained by removing the solvent from the above mixture bydistillation, 10 ml of diethylene glycol and 30 g of potassium hydroxidedissolved in 100 ml of water were added and the reaction was allowed toproceed at 110° C. for over night. After the reaction was completed, amixture of ethyl acetate and water was added to the reaction mixture.After the organic layer was separated, the solvent was removed bydistillation and crude crystals were obtained.

Subsequently, in a 300 ml two-necked flask, the above crude crystals,2.4 g (5 mmole) of Intermediate Compound F, 1.3 g (12 mmole) ofpotassium t-butoxide and 40 mg (5% by mole) of PdCl₂(PPh₃)₂ weredissolved in 30 ml of xylene under an argon stream. The resultingmixture was stirred under heating at 130° C. and the reaction wasallowed to proceed for over night. After the reaction was completed,precipitated crystals were separated by filtration, washed withmethanol, dried and purified by the column chromatography (silica gel,hexaneltoluene=1/1) and 0.2 g of yellow powder was obtained. The powderwas identified to be Compound (59) by the measurements in accordancewith NMR, IR and FD-MS (the yield: 5%).

SYNTHESIS EXAMPLE 10 (COMPOUND (61))

Synthesis of Compound (61)

In a 300 ml four-necked flask, 9.7 g (30 mmole) of4-bromotriphenylamine, 50 ml of toluene and 50 ml of diethyl ether wereplaced and the resulting mixture was cooled with ice water under anargon stream. To the cooled mixture, a mixture of 22 ml (33 mmole) of ahexane solution (1.52 mole/liter) of n-butyllithium and 100 ml oftetrahydrofuran were slowly added dropwise at the room temperature andthe resulting mixture was stirred. After 4.3 g (10 mmole) of6,13-dibromopenthacene was added to the reaction mixture, the obtainedmixture was stirred at the same temperature for one night. After thereaction was completed, 500 ml of water was added to the reactionmixture and the organic layer was extracted with diethyl ether. Theextract was dried with magnesium sulfate and concentrated in vacuo usinga rotary evaporator and 7.4 g of an oily compound was obtained.

In a 300 ml four-necked flask, the above compound, 6.6 g (40 mmole) ofpotassium iodide and 100 ml of acetic acid were placed and the resultingmixture was heated under refluxing for 1 hour. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andprecipitated crystals were separated by filtration. The obtainedcrystals were washed with water and acetone and 2.7 g of orange solidwas obtained. The orange solid was identified to be Compound (61) by themeasurement in accordance with NMR, IR and FD-MS (the yield: 35%).

SYNTHESIS EXAMPLE 11 (COMPOUND (62))

Synthesis of Intermediate Compound G (5,11-diiodonaphthacene)

In a 500 ml round bottom flask, 50 g (0.22 mmole) of naphthacene and 200ml of tetrachloroethane were placed. To this was added 160 g (0.64 mole)of iodine dissolved in 200 ml of carbon tetrachloride slowly dropwise atthe room temperature and the resulting mixture was stirred under heatingfor 5 hours. Precipitated crystals were separated by filtration andwashed with 500 ml of methanol. The obtained crude crystals wererecrystallized from 200 ml of toluene and 34 g of Intermediate CompoundG was obtained (the yield: 40%).

Synthesis of Compound (62)

In a 100 ml four-necked flask, 1.0 g (41 mmole) of magnesium, 1 ml oftetrahydrofuran and a small piece of iodine were placed under an argonstream. To this was added 9.7 g (30 mmole) of 4-bromotriphenylaminedissolved in 100 ml of tetrahydrofuran slowly dropwise at the roomtemperature. After the addition was completed, the resulting mixture wasstirred under heating at 60° C. for 1 hour and a Grignard reagent wasprepared.

In a 300 ml four-necked flask, 4.8 g (10 mmole) of Intermediate CompoundG, 0.28 g (0.4 mmole) of PdCl₂(PPh₃)₂ and 1.0 ml (1 mmole) of a 1.0 Mtoluene solution of AlH(iso-Bu)₂ were dissolved in 50 ml oftetrahydrofuran under an argon stream. To the this mixture, the Grignardreagent prepared above was added dropwise at the room temperature. Thetemperature was elevated and the reaction mixture was heated underrefluxing for one night. After the reaction was completed, the reactionliquid was cooled with ice water. Precipitated crystals were separatedby filtration and washed with acetone. The obtained crude crystals wererecrystallized from 100 ml of acetone and 3.6 g of yellow powder wasobtained. The powder was identified to be Compound (62) by themeasurement in accordance with NMR, IR and FD-MS (the yield: 50%).

EXAMPLE 35

A cleaned glass plate having an ITO electrode was coated with acomposition which contained Compound (58) obtained above as the lightemitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole and apolyearbonate resin (manufactured by TEIJIN KASEI Co., Ltd.; PANLITEK-1300) in amounts such that the ratio by weight was 5:2:2 and wasdissolved in tetrahydrofuran in accordance with the spin coating and alight emitting layer having a thickness of 100 nm was obtained. On theobtained light emitting layer, an electrode having a thickness of 150 nmwas formed with an alloy prepared by mixing aluminum and lithium inamounts such that the content of lithium was 3% by weight and an organicEL device was obtained. The organic EL device emitted yellowish orangelight with a luminance of emitted light of 130 (cd/m²), the maximumluminance of 14,000 (cd/m²) and an efficiency of light emission of 1.2(lm/W) under application of a direct current voltage of 5 V.

EXAMPLE 36

On a cleaned glass plate having an ITO electrode, Compound (71) obtainedabove was vacuum vapor deposited as the light emitting material and alight emitting layer having a thickness of 100 nm was prepared. On theobtained light emitting layer, an electrode having a thickness of 100 nmwas formed with an alloy prepared by mixing aluminum and lithium inamounts such that the content of lithium was 3% by weight and an organicEL device was obtained. The light emitting layer was formed by vapordeposition under a vacuum of 10⁻⁶ Torr while the temperature of thesubstrate was kept at the room temperature. The organic EL deviceemitted orange light with a luminance of emitted light of 120 (cd/m²),the maximum luminance of 1,800 (cd/m²) and an efficiency of lightemission of 0.3 (lm/W) under application of a direct current voltage of5 V.

EXAMPLE 37

On a cleaned glass plate having an ITO electrode, Compound (71) obtainedabove was vacuum vapor deposited as the light emitting material and alight emitting layer having a thickness of 50 nm was prepared. Then, thecompound (Alq) described above was vacuum vapor deposited on theobtained light emitting layer and an electron injection layer having athickness of 10 nm was formed. On the formed layer, an electrode havinga thickness of 100 nm was formed with an alloy prepared by mixingaluminum and lithium in amounts such that the content of lithium was 3%by weight and an organic EL device was obtained. The light emittinglayer and the electron injecting layer were formed by vapor depositionunder a vacuum of 10⁻⁶ Torr while the temperature of the substrate waskept at the room temperature. The organic EL device emitted orange lightwith a luminance of emitted light of about 200 (cd/m²), the maximumluminance of 12,000 (cd/m²) and an efficiency of light emission of 1.0(lm/W) under application of a direct current voltage of 5 V.

EXAMPLES 38 TO 46

On a cleaned glass plate having an ITO electrode, a light emittingmaterial shown in Table 3 was vacuum vapor deposited and a lightemitting layer having a thickness of 80 nm was prepared. Then, thecompound (Alq) described above was vacuum vapor deposited on theobtained light emitting layer and an electron injecting layer having athickness of 20 nm was formed. On the formed layer, an electrode havinga thickness of 150 nm was formed with an alloy prepared by mixingaluminum and lithium in amounts such that the content of lithium was 3%by weight. In this manner, organic EL devices were obtained. The abovelayers were formed by vapor deposition under a vacuum of 10⁻⁶ Torr whilethe temperature of the substrate was kept at the room temperature. Theproperties of light emission of the obtained organic EL devices areshown in Table 3. The organic EL devices in these Examples all showedexcellent luminances such as the maximum luminance of 5,000 (cd/m²) orgreater. TABLE 3 Efficiency of Type of light light emission Half lifetime Example emitting material (lm/W) (hour) 38 (59) 1.2 1400 39 (60)1.4 1600 40 (61) 0.7 1700 41 (62) 0.8 850 42 (65) 0.4 1200 43 (67) 0.61700 44 (70) 1.6 2400 45 (72) 1.2 1600 46 (74) 0.5 1200

EXAMPLE 47

On a cleaned glass plate having an ITO electrode, the compound (TPD74)described above was vacuum vapor deposited as the hole injectingmaterial and a layer having a thickness of 60 nm was formed. Then, thecompound (NPD) described later was vapor deposited as the holetransporting material and a layer having a thickness of 20 nm wasformed.

Then, 4,4′-bis(2,2-diphenylvinyl)biphenyl (DPVBi) and Compound (58)described above were simultaneously vacuum deposited as the lightemitting materials and a layer having a content of Compound (58) of 5%by weight and a thickness of 40 nm was formed. Compound (58) worked alsoas a fluorescent dopant. Then, the compound (Alq) described above wasvapor deposited as the election injection material and a layer having athickness of 20 nm was formed. On the formed layer, lithium fluoride wasvapor deposited and a layer having a thickness of 0.5 nm was formed.Then, aluminum was vapor deposited and a layer having a thickness of 100nm was formed. Thus, an electrode was formed and an organic EL devicewas obtained. The above layers were formed by vapor deposition under avacuum of 10⁻⁶ Torr while the temperature of the substrate was kept atthe room temperature. The organic EL device emitted yellow light with aluminance of emitted light of about 600 (cd/m²) under application of adirect current voltage of 5 V. When the organic EL device was driven bya constant electric current at an initial luminance of emitted light of400 (cd/m²), the half life time was as long as 2,800 hours.

EXAMPLE 48

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 47 except that the light emitting layerwas formed by simultaneously vapor depositing the compound (Alq)described above as the light emitting material and Compound (61)described above as the dopant and a light emitting layer having thecontent of Compound (61) of 5% by weight was formed. The organic ELdevice emitted red light with a luminance of emitted light of about 240(cd/m²) under application of a direct current voltage of 5 V. When theorganic EL device was driven by a constant electric current at aninitial luminance of emitted light of 400 (cd/m²), the half life timewas as long as 3,200 hours.

COMPARATIVE EXAMPLE 5

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 35 except that (Compound of ComparativeExample 1) described above was used as the light emitting material.

The organic EL device exhibited luminance of emitted light of about 60(cd/m²) and an efficiency of light emission of 0.34 (lm/W) underapplication of a direct current voltage of 5 V. Sufficient propertiescould not be obtained. The emitted light was blue light.

COMPARATIVE EXAMPLE 6

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 37 except that (Compound of ComparativeExample 2) described above was used as the light emitting material.

The organic EL device exhibited a luminance of emitted light of about200 (cd/m²) and an efficiency of light emission of 1.2 (lm/W) underapplication of a direct current voltage of 5 V. However, when theorganic EL device was driven by a constant electric current at aninitial luminance of emitted light of 400 (cd/m²), the half life timewas as short as 600 hours. The emitted light was blue light.

COMPARATIVE EXAMPLE 7

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 47 except that (Compound of ComparativeExample 1) described above was used in place of Compound (58).

The organic EL device exhibited a luminance of emitted light of about200 (cd/m²) under application of a direct current voltage of 5 V.However, when the organic EL device was driven by a constant electriccurrent at an initial luminance of emitted light of 400 (cd/m²), thehalf life time was as short as 700 hours. The emitted light was bluelight.

SYNTHESIS EXAMPLE 12 (COMPOUND (75))

Synthesis of Compound (75)

In a 200 ml three-necked flask, 2.16 g (5.5 mmole) of6,12-dibromonaphthacene (40577-78-4), 0.06 g (0.3 mmole) of Pd(OAc)₂,0.23 g (1.1 mmole) of P(tBu)₃, 1.51 g (15.7 mmole) of NaOtBu and 1.89 g(11.2 mmole) of Ph₂NH were dissolved in 25 ml of toluene under an argonstream. The resulting mixture was stirred under heating at 120° C. andthe reaction was allowed to proceed for 7 hours. After the reaction wascompleted, the reaction mixture was left standing and cooled. After redcrystals were separated by filtration, the crystals were washed withtoluene and water and dried in vacuo and 3.02 g of red powder wasobtained. The powder was identified to be Compound (75) by themeasurements in accordance with NMR, IR and FD-MS (the yield: 96%). Thedata obtained in NMR (CDCl₃, TMS) were as follows: 6.8˜7.0 (m, 2H),7.0˜7.4 (m, 10H), 7.8˜7.9 (m, 1H), 8.0˜8.1 (m, 1H) and 8.85 (s, 1H).

EXAMPLE 49

On a cleaned glass plate having an ITO electrode, Compound (TPD74)described above was vacuum vapor deposited as the hole injectingmaterial and a layer having a thickness of 60 nm was formed. Then, thecompound (NPD) described above was vacuum vapor deposited as the holetransporting material and a layer having a thickness of 20 nm wasformed.

Then, the compound (Alq) described above as the light emitting materialand Compound (75) described above as the dopant were simultaneouslyvapor deposited and a layer having a content of Compound (75) of 2% byweight and a thickness of 40 nm was formed. Then, the compound (Alq)described above was vapor deposited as the electron injecting materialand a layer having a thickness of 20 nm was formed. After lithiumfluoride was vapor deposited and a layer having a thickness of 20 nm wasformed, aluminum was vapor deposited and a layer having a thickness of100 nm was formed. Thus, an electrode was formed and an organic ELdevice was prepared. The above layers were formed by vapor depositionunder a vacuum of 10⁻⁶ Torr while the temperature of the substrate waskept at the room temperature. The organic EL device exhibited aluminance of emitted light as high as 500 (cd/m²) under application of adirect current voltage of 8 V and the emitted light was orange light.The organic EL device exhibited a luminance of emitted light as high as500 (cd/m²) under application of a direct current voltage of 8 V and theemitted light was orange light. When the organic EL device was driven bya constant electric current at an initial luminance of emitted light of500 (cd/m²), the organic EL device had a particularly long half lifetime, which was longer than 2,000 hours.

EXAMPLE 50

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 49 except that Compound (86) describedabove was used as the dopant in place of Compound (75). When the organicEL device was driven by a constant electric current at an initialluminance of emitted light of 500 (cd/m²), the organic EL device had ahalf life time as long as 2,000 hours. The emitted light was vermilionlight.

EXAMPLE 51

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 49 except that Compound (82) describedabove was used as the dopant in place of Compound (75). The organic ELdevice exhibited an initial luminance of emitted light of 500 (cd/m²)and the organic EL device had a half life time as long as 2,800 hours orlonger when the organic EL device was driven by a constant electriccurrent. The emitted light was red light.

SYNTHESIS EXAMPLE 13 (COMPOUND (100))

Synthesis of Intermediate Compound H

In a 1 liter three-necked flask equipped with a condenser, 22.7 g (0.1mole) of 4-bromophthalic anhydride and 42.4 g (0.4 mole) of sodiumcarbonate were suspended in 300 ml of water and the components weredissolved by heating at 60° C. under an argon stream. After the mixturewas dissolved, the resulting mixture was cooled to the room temperature.To the cooled mixture, 18.3 g (0.15 mole) of phenylboric acid and 0.7 g(3% by mole) of palladium acetate were added and the obtained mixturewas stirred at the room temperature for one night. After the reactionwas completed, separated crystals were dissolved by adding water. Afterthe catalyst was removed by filtration, crystals were precipitated byadding concentrated hydrochloric acid. The crystals were separated byfiltration and washed with water. The obtained crystals was dissolved inethyl acetate and the organic layer was extracted. The extract was driedwith magnesium sulfate and concentrated in vacuo using a rotaryevaporator and 23.7 g (the yield: 98%) of Intermediate Compound H of theobject compound was obtained.

Synthesis of Intermediate Compound I

In a 500 ml flask having an egg plant shape and equipped with acondenser, 23.7 g (98 mmole) of Intermediate Compound H and 200 ml ofacetic anhydride were placed and the resulting mixture was stirred at80° C. for 3 hours. After the reaction was completed, acetic anhydridein an excess amount was removed by distillation and 22 g (the yield:10%) of Intermediate Compound I of the object compound was obtained.

Synthesis of Intermediate Compound J

In a 500 ml three-necked flask equipped with a condenser, 7.7 g (50mmole) of biphenyl, 13.4 g (0.1 mole) of anhydrous aluminum chloride and200 ml of 1,2-dichloroethane were placed under an argon stream and theresulting mixture was cooled to 0° C. To the cooled mixture, 22 g (98mmole) of Intermediate Compound I was slowly added and the resultingmixture was stirred at 40° C. for 2 hours. After the reaction wascompleted, ice water was added to the reaction mixture and the resultingmixture was extracted with chloroform. The extract was dried withmagnesium sulfate and concentrated in vacuo using a rotary evaporatorand 19.0 g (the yield: 100%) of Intermediate Compound J of the objectcompound was obtained.

Synthesis of Intermediate Compound K

In a 500 ml flask having an egg plant shape and equipped with acondenser, 200 ml of polyphosphoric acid was placed and heated to 150°C. Then, 19 g (50 mmole) of Intermediate Compound J was added in smallportions and the resulting mixture was stirred at the same temperaturefor 3 hours. After the reaction was completed, ice water was added tothe reaction mixture and the resulting mixture was extracted withchloroform. The extract was dried with magnesium sulfate andconcentrated in vacuo using a rotary evaporator. The obtained crudecrystals were purified in accordance with the column chromatography(silica gel, chloroform/methanol=99/1) and 19 g (the yield: 55%) ofIntermediate Compound K of the object compound was obtained.

Synthesis of Intermediate Compound L

In a 500 ml flask having an egg plant shape and equipped with acondenser, 19.0 g (28 mmole) of Intermediate Compound K, 0.19 g (1mmole) of tin chloride, 100 ml of acetic acid and 50 ml of concentratedhydrochloric acid were placed under an argon stream and the resultingmixture was heated under refluxing for 2 hours. After the reaction wascompleted, the reaction mixture was cooled with ice water andprecipitated crystals were separated, washed with water to give 19 g(the yield: 100%) of Intermediate Compound L of the object compound.

Synthesis of Intermediate Compound M

In a 500 ml three-necked flask equipped with a condenser, 19.0 g (28mmole) of Intermediate Compound L, 16 g (60 mmole) of triphenylphosphineand 200 ml of dimethylformamide were placed under an argon stream. Tothis was added 9.6 g (60 mmole) of iodine dissolved in 50 ml ofdimethylformamide slowly dropwise and the resulting mixture was stirredunder heating at 200° C. for 8 hours. After the reaction was completed,the reaction mixture was cooled with ice water and precipitated crystalswere separated. The obtained crystals were washed with water andmethanol and 6.7 g (the yield: 50%) of Intermediate Compound M of theobject compound was obtained.

Synthesis of Compound (100)

In a 200 ml three-necked flask equipped with a condenser, 4.9 g (10mmole) of Intermediate Compound M, 5.1 g (30 mmole) of diphenylamine,0.14 g (1.5% by mole) of tris(dibenzylideneacetone)-dipalladium, 0.91 g(3% by mole) of tri-o-toluylphosphine, 2.9 g (30 mmole) of sodiumt-butoxide and 50 ml of dry toluene were placed under an argon stream.The resulting mixture was stirred overnight under heating at 100° C.After the reaction was completed, precipitated crystals were separatedby filtration and washed with 100 ml of methanol and 4.0 g of yellowpowder was obtained. The obtained powder was identified to be Compound(100) by the measurements in accordance with NMR, IR and FD-MS (theyield: 60%).

The chemical structures of Intermediate Compounds and the route ofsynthesis of Compound (100) are shown in the following.

SYNTHESIS EXAMPLE 14 (COMPOUND (101))

Synthesis of Intermediate Compound N

In a 500 ml flask having an egg plant shape and equipped with acondenser, 12 g (50 mmole) of 2,6-dihydroxyanthraquinone, 42.5 g (0.3mole) of methyl iodide, 17 g (0.3 mole) of potassium hydroxide and 200ml of dimethylsulfoxide were placed under an argon stream and theresulting mixture was stirred at the room temperature for 2 hours. Afterthe reaction was completed, precipitated crystals were separated byfiltration. The obtained crystals were washed with 100 ml of methanoland 10.7 g (the yield: 80%) of Intermediate Compound N of the objectcompound was obtained.

Synthesis of Intermediate Compound O

In a 500 ml three-necked flask equipped with a condenser, 10.7 g (40mmole) of Intermediate Compound N and 200 ml of dry tetrahydrofuran wereplaced under an argon stream and the resulting mixture was cooled to−40° C. To the cooled mixture, 53 ml (80 mmole) of a 1.5 M hexanesolution of phenyllithium was added slowly dropwise. After the additionwas completed, the reaction mixture was stirred at the room temperaturefor one night. After the reaction was completed, precipitated crystalswere separated by filtration and washed with 100 ml of methanol and 100ml of acetone. The obtained crude crystals of a diol was used in thefollowing reaction without further purification.

In a 500 ml flask having an egg plant shape and equipped with acondenser, the crude crystals obtained above, 100 ml of a 57% aqueoussolution of hydrogen iodide and 200 ml of acetic acid were placed andthe resulting mixture was heated under refluxing for 3 hours. After thereaction was cooled to the room temperature, a small amount ofhypophosphorous acid was added to quench hydrogen iodide in an excessamount. Precipitated crystals were separated by filtration and washedwith 100 ml of water, 100 ml of methanol and 100 ml of acetone,successively, and 10.1 g (the yield: 70%) of Intermediate Compound O ofthe object compound was obtained.

Synthesis of Intermediate Compound P

In a 500 ml flask having an egg plant shape and equipped with acondenser, 10.1 g (28 mmole) of Intermediate Compound O, 7.9 g (30mmole) of triphenylphosphine and 200 ml of dimethylformamide were placedunder an argon stream. To the resulting mixture, 4.8 g (30 mmole) ofbromine dissolved in 50 ml of dimethylformamide was slowly addeddropwise and the obtained mixture was stirred under heating at 200° C.for 8 hours. After the reaction was completed, the reaction mixture wascooled with ice water and precipitated crystals were separated byfiltration. The obtained crystals were washed with water and methanoland 8.2 g (the yield: 60%) of Intermediate Compound P of the objectcompound was obtained.

Synthesis of Compound (101)

In a 200 ml three-necked flask equipped with a condenser, 4.9 g (30mmole) of Intermediate Compound P, 5.1 g (30 mmole) of diphenylamine,0.14 g (1.5% by mole) of tris(dibenzylideneacetone) dipalladium, 0.91 g(3% by mole) of tri-o-toluylphosphine, 2.9 g (30 mmole) of sodiumt-butoxide and 50 ml of dry toluene were placed under an argon stream.The resulting mixture was stirred overnight under heating at 100° C.After the reaction was completed, precipitated crystals were separatedby filtration and washed with 100 ml of methanol and 4.0 g of yellowpowder was obtained. The obtained powder was identified to be Compound(101) by the measurements in accordance with NMR, IR and FD-MS (theyield: 60%).

The chemical structures of Intermediate Compounds and the route ofsynthesis of Compound (101) are shown in the following.

SYNTHESIS EXAMPLE 15 (COMPOUND (93))

Synthesis of Intermediate Compound Q

In a 300 ml three-necked flask equipped with a condenser, 11.7 g (50mmole) of 2-bromobiphenyl, 19 g (0.2 mole) of aniline, 0.69 g (1.5% bymole) of tris(dibenzylideneacetone)dipalladium, 0.46 g (3% by mole) oftri-o-toluylphosphine, 7.2 g (75 mmole) of sodium t-butoxide and 100 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration and washedwith 100 ml of methanol. The obtained crude crystals were recrystallizedfrom 50 ml of ethyl acetate and 9.8 g (the yield: 80%) of IntermediateCompound Q of the object compound was obtained.

Synthesis of Compound (93)

In a 200 ml three-necked flask equipped with a condenser, 2.4 g (10mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of Intermediateompound Q, 0.14 g (1.5% by mole) oftris(dibenzylidene-acetone)dipalladium, 0.91 g (3% by mole) oftri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration and washedwith 100 ml of methanol and 4.3 g of yellow powder was obtained. Theobtained powder was identified to be Compound (93) by the measurementsin accordance with NMR, IR and FD-MS (the yield: 65%).

The chemical structure of Intermediate Compound and the route ofsynthesis of Compound (93) are shown in the following.

SYNTHESIS EXAMPLE 16 (COMPOUND (95))

Synthesis of Intermediate Compound R

In a 1 liter three-necked flask equipped with a condenser, 34 g (0.2mole) of 3-phenylphenol, 58 g (0.22 mmole) of triphenylphosphine and 300ml of dimethylformamide were placed under an argon stream. To theresulting mixture, 35 g (0.22 mmole) of bromine dissolved in 100 ml ofdimethylformamide was slowly added dropwise and the obtained mixture wasstirred at 200° C. for 8 hours After the reaction was completed, thereaction mixture was cooled with ice water and precipitated crystalswere separated by filtration. The obtained crystals were washed withwater and methanol and 37 g (the yield: 80%) of Intermediate Compound Rof the object compound was obtained.

Synthesis of Intermediate Compound S

In a 300 ml three-necked flask equipped with a condenser, 19 g (0.2mmole) of aniline, 0.69 g (1.5% by mole) oftris(dibenzylidene-acetone)dipalladium, 0.46 g (3% by mole) oftri-o-toluylphosphine, 7.2 g (75 mmole) of sodium t-butoxide and 100 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration and washedwith 100 ml of methanol. The obtained crude crystals were recrystallizedfrom 50 ml of ethyl acetate and 9.8 g (the yield: 80%) of IntermediateCompound S of the object compound was obtained.

Synthesis of Compound (95)

In a 200 ml three-necked flask equipped with a condenser, 2.4 g (10mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of IntermediateCompound S, 0.14 g (1.5% by mole) oftris(dibenzylidene-acetone)dipalladium, 0.91 g (3% by mole) oftri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration and washedwith 100 ml of methanol and 4.2 g of yellow powder was obtained. Theobtained powder was identified to be Compound (95) by the measurementsin accordance with NMR, IR and FD-MS (the yield: 70%).

The chemical structures of Intermediate Compounds and the route ofsynthesis of Compound (95) are shown in the following.

SYNTHESIS EXAMPLE 17 (COMPOUND (104))

Synthesis of Intermediate Compound T

In a 300 ml three-necked flask equipped with a condenser, 23 g (0.1mole) of 4-bromobiphenyl, 9.8 g (50 mmole) of aminostilbene, 0.69 g(1.5% by mole) of tris(dibenzylideneacetone)dipalladium, 0.46 g (3% bymole) of tri-o-toluylphosphine, 7.2 g (75 mmole) of sodium t-butoxideand 100 ml of dry toluene were placed under an argon stream. Theresulting mixture was stirred overnight under heating at 100° C. Afterthe reaction was completed, precipitated crystals were separated byfiltration and washed with 100 ml of methanol. The obtained crudecrystals were recrystallized from 50 ml of ethyl acetate and 13.9 g (theyield: 80%) of Intermediate Compound T of the object compound wasobtained.

Synthesis of Compound (104)

Into a 200 ml three-necked flask equipped with a condenser, 2.4 g (10mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of IntermediateCompound T, 0.14 g (1.5% by mole) of tris(dibenzylideneacetone)dipalladium, 0.91 g (3% by mole) of tri-o-toluylphosphine, 2.9 g(30 mmole) of sodium t-butoxide and 50 ml of dry toluene were placedunder an argon stream. The resulting mixture was stirred overnight underheating at 100° C. After the reaction was completed, precipitatedcrystals were separated by filtration and washed with 100 ml of methanoland 4.5 g of yellow powder was obtained. The obtained powder wasidentified to be Compound (104) by the measurements in accordance withNMR, IR and FD-MS (the yield: 70%).

The chemical structure of Intermediate Compound and the route ofsynthesis of Compound (104) are shown in the following.

SYNTHESIS EXAMPLE 18 (COMPOUND (105))

Synthesis of Intermediate Compound U

In a 500 ml three-necked flask equipped with a condenser, 25 g (0.1mole) of triphenylamine, 18 g (0.1 mole) of N-bromosuccimide, 0.82 g (5%by mole) of 2,2′-azobisisobutyronitrile and 200 ml of dimethylformamidewere placed under an argon stream. The resulting mixture was stirredunder heating at 110° C. for 4 hours. After the reaction was completed,impurities were removed by filtration and the filtrate was concentratedin vacuo using a rotary evaporator. The obtained crude crystals werepurified in accordance with the column chromatography (silica gel,methylene chloride) and 19 g (the yield: 60%) of Intermediate Compound Uof the object compound was obtained.

Synthesis of Intermediate Compound V

In a 1 liter three-necked flask equipped with a condenser, 1.6 g (66mmole) of magnesium, a small piece of iodine and 100 ml oftetrahydrofuran were placed under an argon stream. After the resultingmixture was stirred at the room temperature for 30 minutes, 19 g (60mole) of Intermediate Compound U dissolved in 300 ml of tetrahydrofuranwas added dropwise. After the addition was completed, the reactionmixture was stirred under heating at 60° C. for 1 hour and a Grignardreagent was prepared.

In a 1 liter three-necked flask equipped with a condenser, 42 g (0.18mmole) of 1,3-dibromobenzene, 2.1 (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 6 ml (6 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 200 ml oftetrahydrofuran were placed under an argon stream. To the mixture, theGrignard reagent prepared above was added dropwise and the obtainedmixture was stirred under heating for one night. After the reaction wascompleted, the reaction liquid was cooled with ice water. Precipitatedcrystals were separated by filtration and washed with acetone and 14 g(the yield: 60%) of Intermediate Compound V of the object compound wasobtained.

Synthesis of Compound (105)

In a 500 ml three-necked flask equipped with a condenser, 0.8 g (33mmole) of magnesium, a small piece of iodine and 50 ml oftetrahydrofuran were placed under an argon stream. After the resultingmixture was stirred at the room temperature for 30 minutes, 12 g (30mmole) of Intermediate Compound V dissolved in 100 ml of tetrahydrofuranwas added dropwise. After the addition was completed, the reactionmixture was stirred under heating at 60° C. for 1 hour and a Grignardreagent was prepared.

In a 500 ml three-necked flask equipped with a condenser, 3.4 g (10mmole) of 9,10-dibromoanthracene, 0.4 (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 0.46 g (3% by mole) oftri-o-toluylphosphine, 1 ml (1 mmole) of a 1 M toluene solution ofdiisobutylaluminum hydride and 100 ml of tetrahydrofuran were placedunder an argon stream. To the obtained mixture, the Grignard reagentprepared above was added dropwise at the room temperature and theresulting mixture was refluxed overnight. After the reaction wascompleted, the reaction liquid was cooled with ice water. Precipitatedcrystals were separated by filtration and washed with 50 ml of methanoland 50 ml of acetone, successively, and 4.1 g of yellow powder wasobtained. The obtained powder was identified to be Compound (105) by themeasurements in accordance with NMR, IR and FD-MS (the yield: 50%).

The chemical structures of Intermediate Compounds and the route ofsynthesis of Compound (105) are shown in the following.

SYNTHESIS EXAMPLE 19 (COMPOUND (122))

Synthesis of Intermediate Compound W

In a 300 ml three-necked flask equipped with a condenser, 19 g (80mmole) of 1,3-dibromobenzene, 6.5 g (20 mmole) of diphenylamine, 0.27 g(1.5% by mole) of tris(dibenzylideneacetone)dipalladium, 0.18 g (3% bymole) of tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxideand 100 ml of dry toluene were placed under an argon stream. Theresulting mixture was stirred overnight under heating at 100° C. Afterthe reaction was completed, precipitated crystals were separated byfiltration and washed with 100 ml of methanol. The obtained crudecrystals were recrystallized from 50 ml of ethyl acetate and 4.9 g (theyield: 75%) of Intermediate Compound W of the object compound wasobtained.

Synthesis of Compound (122)

In a 300 ml three-necked flask equipped with a condenser, 0.5 g (20mmole) of magnesium, a small piece of iodine and 50 ml oftetrahydrofuran were placed under an argon stream. After the resultingmixture was stirred at the room temperature for 30 minutes, 4.9 g (15mmole) of Intermediate Compound W dissolved in 100 ml of tetrahydrofuranwas added dropwise. After the addition was completed, the reactionmixture was stirred under heating at 60° C. for 1 hour and a Grignardreagent was prepared.

In a 500 ml three-necked flask equipped with a condenser, 1.7 g (5mmole) of 9,10-dibromoanthracene, 0.2 g (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 100 ml oftetrahydrofuran were placed under an argon stream. To the mixture, theGrignard reagent prepared above was added dropwise at the roomtemperature and the resulting mixture was stirred overnight underheating. After the reaction was completed, the reaction liquid wascooled with ice water. Precipitated crystals were separated byfiltration and washed with 50 ml of methanol and 50 ml of acetone,successively, and 1.7 g of yellow powder was obtained. The obtainedpowder was identified to be Compound (122) by the measurements inaccordance with NMR, IR and FD-MS (the yield: 50%).

The chemical structure of Intermediate Compound and the route ofsynthesis of Compound (122) are shown in the following.

SYNTHESIS EXAMPLE 20 (COMPOUND (123))

Synthesis of Intermediate Compound X

In a 300 ml three-necked flask equipped with a condenser, 16 g (0.1mole) of bromobenzene, 9.8 g (50 mmole) of aminostilbene, 0.69 g (1.5%by mole) of tris(dibenzylideneacetone)dipalladium, 0.46 g (3% by mole)of tri-o-toluylphosphine, 7.2 g (75 mmole) of sodium t-butoxide and 100ml of dry toluene were placed under an argon stream. The resultingmixture was stirred overnight under heating at 100° C. After thereaction was completed, precipitated crystals were separated byfiltration and washed with 100 ml of methanol. The obtained crudecrystals were recrystallized from 50 ml of ethyl acetate and 11 g (theyield: 80%) of Intermediate Compound X of the object compound wasobtained.

Synthesis of Intermediate Compound Y

In a 500 ml three-necked flask equipped with a condenser, 38 g (0.16mole) of bromobenzene, 11 g (40 mmole) of Intermediate Compound X, 0.55g (1.5% by mole) of tris(dibenzylideneacetone)-dipalladium, 0.37 g (3%by mole) of tri-o-toluylphosphine, 5.8 g (60 mmole) of sodium t-butoxideand 300 ml of dry toluene were placed under an argon stream. Theresulting mixture was stirred overnight under heating at 120° C. Afterthe reaction was completed, precipitated crystals were separated byfiltration and washed with 100 ml of methanol. The obtained crudecrystals were recrystallized from 50 ml of ethyl acetate and 13 g (theyield: 75%) of Intermediate Compound Y of the object compound wasobtained.

Synthesis of Compound (123)

In a 300 ml three-necked flask equipped with a condenser, 0.97 g (40mmole) of magnesium, a small piece of iodine and 50 ml oftetrahydrofuran were placed under an argon stream. After the resultingmixture was stirred at the room temperature for 30 minutes, 12 g (30mole) of Intermediate Compound Y dissolved in 100 ml of tetrahydrofuranwas added dropwise. After the addition was completed, the reactionmixture was stirred under heating at 60° C. for 1 hour and a Grignardreagent was prepared.

In a 500 ml three-necked flask equipped with a condenser, 3.4 g (10mmole) of 9,10-dibromoanthracene, 0.4 g (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 1 ml (1 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 100 ml oftetrahydrofuran were placed under an argon stream. To the obtainedmixture, the Grignard reagent prepared above was added dropwise at theroom temperature and the resulting mixture was refluxed overnight. Afterthe reaction was completed, the reaction liquid was cooled with icewater. Precipitated crystals were separated by filtration and washedwith 50 ml of methanol and 50 ml of acetone, successively, and 5.4 g ofyellow powder was obtained. The obtained powder was identified to beCompound (123) by the measurements in accordance with NMR, IR and FD-MS(the yield: 50%).

The chemical structures of Intermediate Compounds and the route ofsynthesis of Compound (123) are shown in the following.

SYNTHESIS EXAMPLE 21 (COMPOUND (124))

Synthesis of Compound (124)

In a 500 ml three-necked flask equipped with a condenser, 2.5 g (5mmole) of 10,10′-dibromo-9,9′-bianthryl, 0.2 g (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 100 ml oftetrahydrofuran were placed under an argon stream. To the mixture, theGrignard reagent prepared in Synthesis Example 19 was added dropwise atthe room temperature and the resulting mixture was refluxed overnight.After the reaction was completed, the reaction liquid was cooled withice water. Precipitated crystals were separated by filtration and washedwith 50 ml of methanol and 50 ml of acetone, successively, and 2.0 g ofyellow powder was obtained. The obtained powder was identified to beCompound (124) by the measurements in accordance with NMR, IR and FD-MS(the yield: 60%).

The route of synthesis of Compound (124) is shown in the following.

SYNTHESIS EXAMPLE 22 (COMPOUND (125))

Synthesis of Compound (125)

In a 500 ml three-necked flask equipped with a condenser, 1.9 g (5mmole) of 6,12-dibromochrysene, 0.2 g (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 100 ml oftetrahydrofuran were placed under an argon stream. To the mixture, theGrignard reagent prepared in Synthesis Example 19 was added dropwise atthe room temperature and the resulting mixture was stirred under heatingovernight. After the reaction was completed, the reaction liquid wascooled with ice water. Precipitated crystals were separated byfiltration and washed with 50 ml of methanol and 50 ml of acetone,successively, and 2.1 g of yellow powder was obtained. The obtainedpowder was identified to be Compound (125) by the measurements inaccordance with NMR, IR and FD-MS (the yield: 60%).

The route of synthesis of Compound (125) is shown in the following.

SYNTHESIS EXAMPLE 23 (COMPOUND (126))

Synthesis of Compound (126)

In a 500 ml three-necked flask equipped with a condenser, 1.9 g (5mmole) of 5,12-dibromonaphthacene, 0.2 g (5% by mole) ofdichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1 Mtoluene solution of diisobutylaluminum hydride and 100 ml oftetrahydrofuran were placed under an argon stream. To the mixture, theGrignard reagent prepared in Synthesis Example 19 was added dropwise atthe room temperature and the resulting mixture was stirred under heatingovernight. After the reaction was completed, the reaction liquid wascooled with ice water. Precipitated crystals were separated byfiltration and washed with 50 ml of methanol and 50 ml of acetone,successively, and 2.1 g of yellow powder was obtained. The obtainedpowder was identified to be Compound (126) by the measurements inaccordance with NMR, IR and FD-MS (the yield: 60%).

The route of synthesis of Compound (126) is shown in the following.

EXAMPLE 52

On a glass substrate having a size of 25 mm×75 mm×1.1 mm, a transparentanode of a film of indium tin oxide having a thickness of 100 nm wasformed and cleaned for 10 minutes by using ultraviolet light and ozonein combination.

This glass substrate was placed into an apparatus for vacuum vapordeposition (manufactured by NIPPON SHINKUU GIJUTU Co., Ltd.) and thepressure was reduced to about 10⁻⁴ Pa. TPD74 described above was vapordeposited at a speed of 0.2 nm/second and a layer having a thickness of60 nm was formed. Then, TPD78 having the structure shown below was vapordeposited at a speed of 0.2 nm/second and a layer having a thickness of20 nm was formed.

On the layer formed above, DPVDPAN having the structure shown below andCompound (100) described above as the light emitting material weresimultaneously vapor deposited and a light emitting layer having athickness of 40 nm was formed. The speed of vapor deposition of DPVDPANwas 0.4 nm/second and the speed of vapor deposition of Compound (100)was 0.01 nm/second. On the layer formed above, Alq described above wasvapor deposited at a speed of 0.2 nm/second. Finally, aluminum andlithium were vapor deposited simultaneously and a cathode having athickness of 150 nm was formed. Thus, an organic EL device was obtained.The speed of vapor deposition of aluminum was 1 nm/second and the speedof vapor deposition of lithium was 0.004 nm/second.

The properties of the obtained organic EL device were evaluated.Luminance of emitted light at the voltage shown in Table 4 was measuredand the efficiency of light emission was calculated. The color ofemitted light was observed. The organic EL device was driven by aconstant electric current under a nitrogen stream at an initialluminance of emitted light of 500 (cd/m²) and the half life time whichwas the time before the luminance decreases to 250 (cd/m²) was measured.The results are shown in Table 4.

EXAMPLES 53 TO 62

Organic EL devices were prepared in accordance with the same proceduresas those conducted in Example 52 except that the compounds shown inTable 4 were used as the light emitting material in place of Compound(100) and the properties were evaluated. The results are shown in Table4.

COMPARATIVE EXAMPLE 8

An organic EL devices was prepared in accordance with the sameprocedures as those conducted in Example 52 except that the diaminecompound shown below was used as the light emitting material in place ofCompound (100) and the properties were evaluated. The results are shownin Table 4. TABLE 4

Luminance Efficiency of emitted of light Half life Color Voltage lightemission time of emitted (V) (cd/m²) (lm/W) (hour) light Example 52 6.0120 4.50 1800 green 53 6.0 240 3.90 2000 bluish green 54 6.0 130 4.601700 green 55 6.0 210 4.90 2500 green 56 7.0 230 4.00 1500 yellowishgreen 57 6.0 120 2.90 2100 blue 58 6.0 180 3.40 1800 bluish greem 59 5.5220 4.62 1700 blue 60 5.5 420 3.10 2200 bluish green 61 5.5 180 4.253100 blue 62 5.0 2240 4.90 3200 bluish green Comparative Example 8 6.0150 3.70 1200 green

As shown in Table 4, the organic EL devices of Examples 52 to 62 inwhich the compounds represented by general formulae [9] and [10] of thepresent invention were used as the light emitting material or the holetransporting material exhibited more excellent luminance of emittedlight and efficiencies of light emission and longer lives in comparisonwith the organic EL device of Comparative Example 8 in which the diaminecompound was used.

SYNTHESIS EXAMPLE 24 (COMPOUND a)

Synthesis of Intermediate Compound A

In a 500 ml three-necked flask, 50 g (0.27 mole) of p-bromobenzaldehyde,50 g (0.22 mmole) of diethyl benzylphosphonate and 200 ml ofdimethylsulfoxide were placed under an argon stream. To this was added30 g (0.27 mole) of potassium t-butoxide in small portions. Theresulting mixture was stirred overnight at the room temperature. Afterthe reaction was completed, the reaction liquid was poured into 500 mlof water and extracted with ethyl acetate. The extract was dried withmagnesium sulfate and concentrated in vacuo using a rotary evaporator.The obtained crude crystals were recrystallized from 100 ml of ethylacetate and 46 g (the yield: 81%) of Intermediate Compound A wasobtained.

Synthesis of Intermediate Compound B

Into a 300 ml three-necked flask equipped with a condenser, 10 g (38mmole) of Intermediate Compound A, 14 g (150 mmole) of aniline, 0.53 g(1.5% by mole) of tris(dibenzylideneacetone)dipalladium, 0.35 g (3% bymole) of tri-o-toluylphosphine, 7.4 g (77 mole) of sodium t-butoxide and100 ml of dry toluene were placed under an argon stream. The resultingmixture was stirred overnight under heating at 100° C. After thereaction was completed, precipitated crystals were separated byfiltration and washed with 100 ml of methanol. The obtained crudecrystals were recrystallized from 50 ml of ethyl acetate and 7.7 g (theyield: 73%) of Intermediate Compound B was obtained.

Synthesis of Intermediate Compound C

In a 100 ml flask having an egg plant shape and equipped with acondenser, 12.5 g (50 mmole) of 4-bromobenzyl bromide and 12.5 (75mmole) of triethyl phosphite were placed. The resulting mixture wasstirred under heating at 100° C. for 7 hours. After the reaction wascompleted, triethyl phosphite in an excess amount was removed bydistillation in vacuo and 15.4 g of Intermediate Compound C wasobtained. Intermediate Compound C was used in the following reactionwithout further purification.

Synthesis of Intermediate Compound D

In a 300 ml three-necked flask, 9.2 g (50 mmole) of p-bromobenzaldehyde,15.4 g (50 mmole) of Intermediate Compound C and 100 ml ofdimethylsulfoxide were placed under an argon stream. To this was added6.7 g (60 mmole) of potassium t-butoxide in small portions and theresulting mixture was stirred overnight at the room temperature. Afterthe reaction was completed, the reaction liquid was poured into 200 mlof water and extracted with ethyl acetate. The extract was dried withmagnesium sulfate and concentrated in vacuo using a rotary evaporator.The obtained crystals were washed with 100 ml of methanol and 13 g (theyield: 77%) of Intermediate compound D was obtained.

Synthesis of Compound a

In a 200 ml three-necked flask equipped with a condenser, 4 g (15 mmole)of Intermediate Compound B, 2 g (6 mmole) of Intermediate Compound D,0.16 g (3% by mole) of tris(dibenzylideneacetone)dipalladium, 0.22 g (6%by mole) of (S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration, washedwith methanol and dried by heating at 60° C. for one night. The obtainedcrude crystals were purified in accordance with the columnchromatography (silica gel, hexane/toluene=8/2) and 1.4 g of yellowpowder was obtained. The obtained powder was identified to be Compound aby the measurements in accordance with NMR, IR and FD-MS (the fielddesorption mass spectroscopy) (the yield: 32%, in ¹H_(NMR) (90 Hz): δ7.0˜7.4 ppm (42H, m)). The NMR chart of Compound a is shown in FIG. 1.

The chemical reactions to obtain Compound a are shown in the following:

SYNTHESIS EXAMPLE 25 (Compound b)

Synthesis of Intermediate Compound E

In a 300 ml three-necked flask, 6 g (50 mmole) of p-tolualdehyde, 15.4 g(50 mmole) of Intermediate Compound C and 100 ml of dimethylsulfoxidewere placed under an argon stream. To this was added 6.7 g (60 mmole) ofpotassium t-butoxide in small portions and the resulting mixture wasstirred overnight at the room temperature. After the reaction wascompleted, the reaction liquid was poured into 200 ml of water andextracted with ethyl acetate. The extract was dried with magnesiumsulfate and concentrated in vacuo using a rotary evaporator. Theobtained crystals were washed with 100 ml of methanol and 9.2 g (theyield: 67%) of Intermediate Compound E was obtained.

Synthesis of Compound b

In a 200 ml three-necked flask equipped with a condenser, 4 g (15 mmole)of Intermediate Compound E, 2 g (6 mmole) of N,N′-diphenylbenzidine,0.16 g (3% by mole) of tris(dibenzylideneacetone) dipalladium, 0.22 g(6% by mole) of (S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50ml of dry toluene were placed under an argon stream. The resultingmixture was stirred overnight under heating at 100° C. After thereaction was completed, precipitated crystals were separated byfiltration, washed with methanol and dried by heating at 60° C. for onenight. The obtained crude crystals were purified in accordance with thecolumn chromatography (silica gel, hexane/toluene=8/2) and 2.5 g ofyellow powder was obtained. The obtained powder was identified to beCompound b by the measurements in accordance with NMR, IR and FD-MS (theyield: 58%, in ¹H_(NMR) (90 Hz): δ 7.0˜7.4 ppm (40H, m), δ 2.34 ppm(6H,s)). The NMR chart of Compound b is shown in FIG. 2.

The chemical reactions to obtain Compound b are shown in the following:

SYNTHESIS EXAMPLE 26 (COMPOUND c)

Synthesis of Compound c

In a 200 ml three-necked flask equipped with a condenser, 4 g (15 mmole)of Intermediate Compound B, 1.7 g (6 mmole) of 1,4-dibromonaphthalene,0.16 g (3% by mole) of tris(dibenzylideneacetone) dipalladium, 0.22 g(6% by mole) of (S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50ml of dry toluene were placed under an argon stream. The resultingmixture was stirred over night under heating at 100° C. After thereaction was completed, precipitated crystals were separated byfiltration, washed with methanol and dried by heating at 60° C. for onenight. The obtained crude crystals were purified in accordance with thecolumn chromatography (silica gel, hexane/toluene=8/2) and 2.0 g ofyellow powder was obtained. The obtained powder was identified to beCompound c by the measurements in accordance with NMR, IR and FD-MS (theyield: 50%, in ¹H_(NMR) (90 Hz): δ 7.0˜7.4 ppm (68H, m)).

The chemical reaction to obtain Compound c is shown in the following:

SYNTHESIS EXAMPLE 27 (COMPOUND d)

Synthesis of Compound d

In a 200 ml three-necked flask equipped with a condenser, 4 g (15 mmole)of Intermediate Compound B, 2 g (6 mmole) of 9,10-dibromoanthracene,0.16 g (3% by mole) of tris(dibenzylideneacetone) dipalladium, 0.07 g(6% by mole) of tri-t-butylphosphine, 1.4 g (15 mmole) of sodiumt-butoxide and 50 ml of dry toluene were placed under an argon stream.The resulting mixture was stirred overnight under heating at 100° C.After the reaction was completed, precipitated crystals were separatedby filtration, washed with methanol and dried by heating at 60° C. forone night. The obtained crude crystals were purified in accordance withthe column chromatography (silica gel, hexane/toluene=8/2) and 1.9 g ofyellow powder was obtained. The obtained powder was identified to beCompound d by the measurements in accordance with NMR, IR and FD-MS (theyield: 44%, in ¹H_(NMR) (90 Hz): δ 7.0˜7.4 ppm (40H, m)).

The chemical reaction to obtain Compound d is shown in the following:

SYNTHESIS EXAMPLE 28 (COMPOUND e)

Synthesis of Intermediate Compound E

In a 300 ml three-necked flask, 10.4 g (50 mmole) oftrans-4-stilbenealdehyde, 15.4 g (50 mmole) of Intermediate Compound Cand 100 ml of dimethylsulfoxide were placed under an argon stream. Tothis was added 6.7 g (60 mmole) of potassium t-butoxide in smallportions and the resulting mixture was stirred overnight at the roomtemperature. After the reaction was completed, the reaction liquid waspoured into 200 ml of water and extracted with ethyl acetate. Theextract was dried with magnesium sulfate and concentrated in vacuo usinga rotary evaporator. The obtained crystals were washed with 100 ml ofmethanol and 12.5 g (the yield: 69%) of Intermediate Compound F wasobtained.

Synthesis of Compound e

In a 200 ml three-necked flask equipped with a condenser, 5.4 g (15mmole) of Intermediate Compound F, 2 g (6 mmole) ofN,N′-diphenylbenzidine, 0.16 g (3% by mole) oftris(dibenzylideneacetone) dipalladium, 0.11 g (6% by mole) oftri-o-toluylphosphine, 1.4 g (15 mmole) of sodium t-butoxide and 50 mlof dry toluene were placed under an argon stream. The resulting mixturewas stirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration, washedwith methanol and dried by heating at 60° C. for one night. The obtainedcrude crystals were purified in accordance with the columnchromatography (silica gel, hexane/toluene=6/4) and 1.0 g of yellowpowder was obtained. The obtained powder was identified to be Compound eby the measurements in accordance with NMR, IR and FD-MS (the yield:19%, in ¹H_(NMR) (90 Hz): δ 7.0-7.5 ppm (52H, m)). The NMR chart ofCompound e is shown in FIG. 3.

The chemical reactions to obtain Compound e are shown in the following:

Synthesis of Compound f

In a 200 ml three-necked flask equipped with a condenser, 7.8 g (30mmole) of Intermediate Compound A, 1.7 g (6 mmole) of 4,4′diaminostilbene carbon dioxide, 0.16 g (3% by mole) oftris(dibenzylidene acetone)dipalladium, 0.22 g (6% by mole) of(S)-BINAP, 9.6 g (0.1 mole) of sodium t-butoxide and 50 ml of drytoluene were placed under an argon stream. The resulting mixture wasstirred overnight under heating at 100° C. After the reaction wascompleted, precipitated crystals were separated by filtration, washedwith methanol and dried by heating at 60° C. for one night. The obtainedcrude crystals were purified in accordance with the columnchromatography (silica gel, hexane/toluene=6/4) and 2.0 g of yellowpowder was obtained. The obtained powder was identified to be Compound fby the measurements in accordance with NMR, IR and FD-MS (the yield:36%, in ¹H_(NMR) (90 Hz): δ 7.0˜7.5 ppm (54H, m)).

The chemical reaction to obtain Compound f is shown in the following:

EXAMPLE 63

On a cleaned glass plate having an ITO electrode, TPD74 described abovewas vacuum vapor deposited as the hole injecting material and a layerhaving a thickness of 60 nm was formed.

Then, NPD described above was vacuum vapor deposited as the holetransporting material and a layer having a thickness of 20 nm wasformed.

Subsequently, as the light emitting materials,4,4′-bis(2,2-diphenylvinyl)biphenyl (DPVBi) which is a stilbenederivative and Compound a described above were simultaneously vapordeposited and a layer having a content of Compound a of 2% by weight anda thickness of 40 nm was formed. Compound a works as a fluorescentdopant or the light emitting center. On the layer formed above, Alqdescribed above was vapor deposited as the electron injecting materialand a layer having a thickness of 20 nm was formed. After lithiumfluoride was vapor deposited and a layer having a thickness of 0.5 nmwas formed, aluminum was vapor deposited and a layer having a thicknessof 100 nm was formed. Thus, an electrode was formed and an organic ELdevice was obtained. The layers were vapor deposited in a vacuum of 10⁻⁶Torr while the substrate was kept at the room temperature. The deviceexhibited a luminance of emitted light of 100 (cd/m²) and an efficiencyof light emission of 2.1 (lm/W) under application of a direct currentvoltage of 6 V. The color coordinate was (0.146, 0.140) and blue lightof a high purity could be emitted. When the organic EL device was drivenby a constant electric current at an initial luminance of emitted lightof 200 (cd/m²), the half life time was as long as 2,000 hours. Theproperties of light emission are shown in Table 5.

The energy gap of Compound a was 2.78 eV and the energy gap of DPVBi was3.0 eV.

EXAMPLE 64

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that Compound b was used as thedopant or the light emitting center. The device exhibited a luminance ofemitted light of 110 (cd/m²) and an efficiency of light emission of 1.3(lm/W) under application of a direct current voltage of 6 V. The colorcoordinate was (0.152, 0.163) and blue light of a high purity could beemitted. When the organic EL device was driven by a constant electriccurrent at an initial luminance of emitted light of 200 (cd/m²), thehalf life time was as long as 1,500 hours. The properties of lightemission are shown in Table 5.

The energy gap of Compound b was 2.90 eV and the energy gap of DPVBi was3.0 eV.

EXAMPLE 65

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that Compound c was used as thedopant or the light emitting center. The device exhibited a luminance ofemitted light of 130 (cd/m²) and an efficiency of light emission of 2.1(lm/W) under application of a direct current voltage of 6 V. The colorcoordinate was (0.162, 0.181) and blue light of a high purity could beemitted. When the organic EL device was driven by a constant electriccurrent at an initial luminance of emitted light of 200 (cd/m²), thehalf life time was as long as 2,800 hours. The properties of lightemission are shown in Table 5.

The energy gap of Compound b was 2.83 eV and the energy gap of DPVBi was3.0 eV.

EXAMPLE 66

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that Compound d was used as thedopant or the light emitting center. The device exhibited a luminance ofemitted light of 300 (cd/m²) and an efficiency of light emission of 4.6(lm/W) under application of a direct current voltage of 6 V. Light ofgreen color could be emitted with a high efficiency. When the organic ELdevice was driven by a constant electric current at an initial luminanceof emitted light of 200 (cd/m²), the half life time was as long as 3,400hours. The properties of light emission are shown in Table 5.

The energy gap of Compound d was 2.78 eV and the energy gap of DPVBi was3.0 eV.

COMPARATIVE EXAMPLE 9

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that the following compound(TPD):

was used as the dopant or the light emitting center. The deviceexhibited a luminance of emitted light of 60 (cd/m²) and an efficiencyof light emission of 0.7 (lm/W) under application of a direct currentvoltage of 5 V. Sufficient properties could not be obtained. TPD did notwork as the light emitting center and light emitted from DPVTP wasobtained. When the organic EL device was driven by a constant electriccurrent at an initial luminance of emitted light of 200 (cd/m²), thehalf life time was as short as 100 hours. The properties of lightemission are shown in Table 5.

The energy gap of TPD was 3.10 eV and the energy gap of DPVBi was 3.0eV.

COMPARATIVE EXAMPLE 10

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that Compound a described abovewas used as the dopant or the light emitting material and the compoundAlq was used as the light emitting material. The device exhibited aluminance of emitted light of 210 (cd/m²) and an efficiency of lightemission of 1.3 (lm/W) under application of a direct current voltage of6 V. However, light of pink color from Alq alone was obtained. When theorganic EL device was driven by a constant electric current at aninitial luminance of emitted light of 200 (cd/m²), the half life timewas as short as 200 hours. The properties of light emission are shown inTable 5. Compound a did not work as the light emitting center.

The energy gap of Compound a was 2.95 eV and the energy gap of Alq was2.7 eV.

COMPARATIVE EXAMPLE 11

An organic EL device was prepared in accordance with the same proceduresas those conducted in Example 63 except that no dopant or light emittingmaterial was used and Compound c described above was used as the singlelight emitting material. The device exhibited luminance of emitted lightof 40 (cd/m²) and an efficiency of light emission of 0.9 (lm/W) underapplication of a direct current voltage of 6 V. Sufficient propertiescould not be obtained. When the organic EL device was driven by aconstant electric current at an initial luminance of emitted light of200 (cd/m²), the half life time was as short as 180 hours. Theproperties of light emission are shown in Table 5.

The properties of light emission obtained above are shown in Table 5.TABLE 4 Dopant or Luminance Efficiency Color light Light Applied ofemitted of light of Half life emitting emitting voltage light emissionemitted time center material (V) (cd/m²) (lm/W) light (hour) Example 63Compound a DPVBi 6 100 2.1 blue 2000 64 Compound b DPVBi 6 110 1.3 blue1500 65 Compound c DPVBi 6 130 2.1 blue 2800 66 Compound d DPVBi 6 3004.6 green 3400 Comparative Example  9 TPD DPVBi 5 60 0.7 blue 100 10Compound a Alq 6 210 1.3 green 200 11 none Compound c 6 40 0.9 blue 180

As shown in Table 5, the organic EL devices of Examples 63 to 66 inwhich a small amount (1 to 20% by weight) of a compound represented bygeneral formula [1] was added to the host material as the dopant or thelight emitting center exhibited higher efficiencies of light emissionand much longer lives in comparison with the organic EL devices ofComparative Examples 9 to 11.

INDUSTRIAL APPLICABILITY

The organic EL devices of the present invention in which the materialsfor organic EL devices represented by general formulae [1], [3] to [6]and [9] to [10] described above are used as the light emitting material,the hole injecting material, the hole transporting material or thedoping material exhibit luminances of light emission sufficient forpractical use and high efficiencies of light emission under applicationof a low voltage, have long lives because the decrease in the propertiesafter use for a long time is suppressed and show no deterioration in theproperties in the environment of high temperatures due to excellent heatresistance.

The organic EL devices described above in which the materials fororganic EL devices represented by general formulae [7] and [8] are usedas the light emitting material, the hole injecting material, the holetransporting material or the doping material exhibit, in the region ofyellow color and orange to red color, luminances of light emissionsufficient for practical use and high efficiencies of light emissionunder application of a low voltage and have long life times because thedecrease in the properties after use for a long time is suppressed.

The organic EL devices in which the material for organic EL devicescomprising the compound represented by general formula [11] of thepresent invention or the novel compound represented by general formula[11′] of the present invention is used as the dopant or the lightemitting center exhibit luminances of emitted light sufficient forpractical use under application of a low voltage and high efficienciesof light emission and have long lives because the decrease in theproperties after use for a long time is suppressed.

By producing materials for organic EL devices in accordance with theprocess of the present invention, materials for organic EL devicesexhibiting a high efficiency of light emission, having a long life,showing high activity and containing little impurities can be producedin a high yield.

1. A material for an organic electroluminescence device represented byfollowing general formula (4):

wherein X¹ to X⁴ each independently represent a substituted orunsubstituted arylene group having 6 to 30 carbon atoms, X¹ and X² maybe bonded to each other, X³ and X⁴ may be bonded to each other, Y¹ to Y⁴each independently represent an organic group represented by generalformula (2), a to d each represent an integer of 0 to 2 with the provisothat a+b+c+d≧0; general formula (2) being:

wherein R¹ to R⁴ are each independently a hydrogen atom, a substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, a substitutedor unsubstituted aryl group having 6 to 20 carbon atoms, cyano group orform a triple bond by a linkage of R¹ and R² or R³ and R⁴, Z representsa substituted or unsubstituted aryl group having 6 to 20 carbon atomsand n represents 0 or
 1. 2. A dopant material for an organicelectroluminescence device represented by following general formula (4):

wherein X¹ to X⁴ each independently represent a substituted orunsubstituted arylene group having 6 to 30 carbon atoms, X¹ and X² maybe bonded to each other, X³ and X⁴ may be bonded to each other, Y¹ to Y⁴each independently represent an organic group represented by generalformula (2), a to d each represent an integer of 0 to 2 with the provisothat a+b+c+d≧0; general formula (2) being:

wherein R¹ to R⁴ are each independently a hydrogen atom, a substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, a substitutedor unsubstituted aryl group having 6 to 20 carbon atoms, cyano group orform a triple bond by a linkage of R¹ and R² or R³ and R⁴, Z representsa substituted or unsubstituted aryl group having 6 to 20 carbon atomsand n represents 0 or
 1. 3. A hole transporting material for an organicelectroluminescence device represented by following general formula (4):

wherein X¹ to X⁴ each independently represent a substituted orunsubstituted arylene group having 6 to 30 carbon atoms, X¹ and X² maybe bonded to each other, X³ and X⁴ may be bonded to each other, Y¹ to Y⁴each independently represent an organic group represented by generalformula (2), a to d each represent an integer of 0 to 2 with the provisothat a+b+c+d≧0; general formula (2) being:

wherein R¹ to R⁴ are each independently a hydrogen atom, a substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, a substitutedor unsubstituted aryl group having 6 to 20 carbon atoms, cyano group orform a triple bond by a linkage of R¹ and R² or R³ and R⁴, Z representsa substituted or unsubstituted aryl group having 6 to 20 carbon atomsand n represents 0 or
 1. 4. The material for an organicelectroluminescence device according to claim 1, wherein in formula (4)a+b+c+c=0.
 5. The dopant material for an electroluminescence deviceaccording to claim 2, wherein in formula (4) a+b+c+d=0.
 6. The holetransporting material for an electroluminescence device according toclaim 3, wherein in formula (4) a+b+c+d=0.
 7. The material for ablue-light emitting organic electroluminescent device comprising thematerial of claim
 1. 8. The dopant material for a blue-light emittingorganic electroluminescent device comprising the material of claim
 2. 9.The hole transporting material for a blue-light emitting organicelectroluminescent device comprising the material of claim 3.